Heating cosmetic treatment process using a particular polyester

ABSTRACT

Non-therapeutic process for making up and/or caring for non-fibrous human keratin materials, especially the skin, its mucous membranes or the nails, by bringing an outer surface of a piece of a particular solid cosmetic composition into contact with or close to a heating device so as to heat the piece locally in order to soften essentially only the outer surface and to lower its coefficient of dynamic friction, and then applying the outer surface of the composition thus heated to the region to be treated.

REFERENCE TO PRIOR APPLICATIONS

This application claims priority to U.S. provisional application Ser. No. 61/300,459, filed Feb. 2, 2010; and to French patent application 10 50442, filed Jan. 22, 2010, both incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to the field of making up and/or caring for human keratin materials and more particularly the skin and/or the lips, and in particular a makeup process comprising a step of heating, prior to application, of a composition comprising at least one particular polyester and a solid fatty substance.

BACKGROUND OF THE INVENTION

The development of formulations, in particular in solid form, intended for making up and/or caring for the skin and/or the lips, which have satisfactory properties in terms of application, especially of glidance and of amount deposited, and whose deposition onto keratin materials (in particular the skin and/or the lips) is satisfactory in terms of gloss, comfort and remanence of the colour, is a permanent objective.

Document FR 2 917 616 discloses cosmetic compositions containing polyesters combined with standard volatile oils such as isododecane, for obtaining, after application to keratin materials, especially the lips, a relatively glossy makeup deposit that shows acceptable remanence properties.

However, it is always desirable to further improve the remanence of the deposit of such compositions when they are applied to keratin materials, in particular such that the deposit formed conserves its integrity and remains homogeneous for 2 or 3 hours, or even for 4 or 6 hours, and does not show any tendency to become brittle or to fragment, in particular on contact with fatty substances, in particular during a meal, or on contact with saliva. Furthermore, in the case of lipstick compositions, it is desirable to improve the gloss of the deposit of such compositions on the lips.

Furthermore, polyesters are very viscous, and the resulting solid compositions are generally very tacky on contact with the skin or the lips, and thus difficult to apply, not making it possible to obtain a thick, uniform deposit. They glide poorly and disintegrate with difficulty.

It is thus sought to obtain solid compositions (which are in particular compatible with conditioning as a wand or in another solid form) comprising such polyesters, which are stable, which are easy to apply (good glidance) on the skin or the lips, and which form a deposit that shows good remanence properties over time, and optionally good gloss properties in the case of lipstick compositions, and which are comfortable.

An object of the invention is, precisely, to provide a novel makeup and/or care method that can satisfy all the abovementioned requirements.

BRIEF DESCRIPTION OF THE DRAWINGS

The description of the present invention is made in part with reference to the attached drawings, in which:

FIG. 1 shows schematically, in elevation, an example of a conditioning and application device made in accordance with the invention,

FIG. 2 shows in isolation, with partial and schematic longitudinal cutaway, the cap of the device of FIG. 1,

FIG. 3 illustrates, schematically and partially, the heating of the wand by contact with a hot surface,

FIG. 4 represents, schematically and partially, one embodiment example of the heating member,

FIGS. 5 to 7 illustrate production details of variants of heating members,

FIG. 8 represents, schematically, an embodiment variant of the conditioning and application device,

FIG. 9 is a schematic and partial cutaway of the device of FIG. 8, after insertion in the corresponding housing of the case,

FIG. 10 shows a wand and associated support means,

FIG. 11 shows in elevation an embodiment variant of the conditioning and application device,

FIG. 12 is a partial and schematic longitudinal cutaway of the device of FIG. 11,

FIG. 13 is a partial and schematic longitudinal cutaway of an embodiment variant of the device,

FIG. 14 is a product conditioning variant, and

FIG. 15 described previously illustrates the measurement of the coefficient of dynamic friction.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Thus, according to a first of its aspects, a subject of the invention is a non-therapeutic process for making up and/or caring for human keratin materials, especially the skin or the lips, in which:

-   -   an outer surface of a piece of cosmetic composition that is         solid at 20° C. is brought into contact with or close to a         heating device so as to heat the piece locally in order to         soften essentially only the outer surface and to lower its         coefficient of dynamic friction, and     -   the outer surface of the composition thus heated is then applied         to the region to be treated, and especially to be made up,         the solid cosmetic composition comprising, in a physiologically         acceptable medium:         (i) at least one polyester that may be obtained by reacting:     -   a tetraol containing from 4 to 10 carbon atoms;     -   a linear or branched saturated monocarboxylic acid containing         from 9 to 23 carbon atoms;     -   a cyclic dicarboxylic acid containing from 6 to 12 carbon atoms;         and     -   an aromatic monocarboxylic acid containing from 7 to 11 carbon         atoms,         (ii) and at least one solid fatty substance chosen from waxes         and pasty fatty substances, and a mixture thereof.

According to one particular embodiment of the invention, the process is a makeup process.

According to one particular embodiment, the softened outer surface is brought into direct contact with the region to be treated, and in particular with the keratin materials.

In other words, no applicator is used to deposit the softened composition.

For the purposes of the present invention, the term “solid” refers to a composition having, at 20° C. and at atmospheric pressure (760 mmHg), a hardness of greater than 30 Nm⁻¹ and preferably greater than 40 Nm⁻¹.

According to one preferred embodiment, the solid composition according to the invention is in the form of a stick. When the composition is in the form of a stick, the outer surface may be defined as the end thereof, i.e. the free end that is applied to the keratin materials by the user.

According to one particular embodiment, the process according to the present invention is such that the composition is in the form of a wand, especially with a diameter of greater than or equal to 7 mm.

According to yet another embodiment, the process according to the present invention is such that the composition is a lipstick.

It is advantageously characterized by a hardness as defined below.

According to yet another aspect, the invention relates to a kit comprising:

-   -   a composition as defined previously, and     -   a heating device for locally heating a surface of a piece of the         composition.

The piece of composition may be permanently in contact with or close to the heating device, and this heating device may be activated before applying the composition, to raise the temperature of the outer surface of the piece of composition. As a variant, the piece of composition is brought into contact with or close to the heating device only for the use, for the purpose of applying the composition.

Thus, the invention may make it possible to heat at the surface, just before application, for example the top of the bevel of a lipstick wand made with a composition according to the invention, so as to allow deposition, even if the wand contains compounds that are sparingly suited to satisfactory cold application, these compounds affording increased performance in terms of staying power and/or gloss.

In examples of implementation of the invention, by heating the surface of the wand, its glidance and thus its application to the lips or the skin may be improved.

According to one particular embodiment, the composition used according to the invention has a temperature-sensitive coefficient of dynamic friction, of greater than or equal to 0.5 at 25° C. and better still greater than or equal to 0.6 at 25° C.

The solid composition advantageously has a hardness of greater than or equal to 80 Nm⁻¹ at 20° C., better still greater than or equal to 100 Nm⁻¹ or even 120 Nm⁻¹ at 20° C., which makes the wand mechanically strong and allows its conditioning, for example, in a conventional case comprising two parts that can rotate relative to each other to move the wand.

The coefficient of dynamic friction may be, at the temperature to which the composition is heated, less than or equal to 0.45 and better still 0.4.

The coefficient of dynamic friction, which is greater than or equal to 0.5 at 25° C. may thus become, for example, less than or equal to 0.45 at 45° C., i.e. it may reach a value comparable to certain known lipsticks intended for application at 25° C.

The invention may apply to a wand of product comprising an amount of polyester such that its application cold and/or without heating is difficult, virtually impossible or unpleasant. For such a wand of product, application after heating becomes possible, with particularly advantageous comfort or even gloss performance with regard to the presence of the oils it contains.

In the context of the invention, it is important for the compositions used to be stable (and in particular for them not to have any problems of phase separation) at room temperature (at 20° C.) and when they are heated before application (especially to a temperature of about 60° C.)

The product may be heated in various ways, for example by being exposed to infrared radiation or to wireless radiation.

The product may also be heated by blowing with hot air, by being exposed to ultrasonic vibrations or by heat transfer on contact with or close to a hot surface which, for example, bears radially against the outer surface, especially the end of the wand. The hot surface may also bear axially against the outer surface, especially the end of the wand. The hot surface may have a beveled, inverted cone or concave hollow shape, especially spherical.

The outer surface of the product may be heated to a temperature T_(f) of greater than or equal to 40° C., or even greater than 45° C. or alternatively greater than 50° C. The outer surface may be heated to a temperature T_(f) of between 40° C. and 95° C., better still 45° C. to 85° C. and better still 45° C. to 75° C.

The temperature of the application surface, especially of the end of the wand, should not lead to any risk of burning at the time of application. This is why a waiting time between the moment at which the end is heated and the application to the keratin materials may optionally be necessary.

The temperature difference between the heated outer surface and the portion of the product that remains solid may be greater than or equal to 5° C. and better still greater than or equal to 15° C. or 20° C., at least at the start of application, or even greater than 30° C.

Only the product may come into contact with the treated area during the application.

The heating device may be housed in a cap for closing the support, so as to allow the outer surface to be heated with the cap in place on the support. The heating device may also be housed elsewhere than in a cap for closing the support.

The heating device may be housed in a case on which the support may be engaged so that the heating may take place when the support is engaged in the case, especially a case comprising an aperture in which the piece of solid product may be engaged, preferably without the whole support being placed inside the case.

The heating device may be an integral part of the conditioning and application device.

The heating device may be arranged to come into contact with the outer surface.

The heating device may be arranged so that the piece of product passes through it, and may especially comprise a circular-shaped hot surface.

The heating device may comprise a control means allowing the user to control its functioning. This control means may comprise a switch present on the support or on a cap for closing the support.

The heating device may comprise an electrical resistance to heat a surface that may come into contact with or close to the application surface.

The heating device may comprise an infrared emitter arranged to subject the application surface to infrared light so as to heat it, and a wireless radiation emission means for raising the temperature of the outer surface, a fan for blowing hot air onto the outer surface or a source of ultrasound for heating the outer surface.

The heating device may also comprise at least two components that are capable, when mixed together, of producing an exothermic reaction.

The piece of product may be in the form of a wand and the outer surface may be defined by the end of the wand.

The heating device may comprise a source of electrical power comprising one or more batteries or accumulators.

The heating device may comprise an electric generator actuated by the user.

The heating device may comprise means for heating the piece of composition to a predefined temperature, despite the wear of the piece. This means may comprise an elastically deformable member, which ensures contact or a constant gap between the outer surface to be heated and the heating device, by compensating for the wear of the piece of composition.

These means may also comprise, where appropriate, a temperature sensor for adjusting the heating power, for example for increasing it if the outer surface is further away from the source of heat.

Coefficient of Dynamic Friction

To characterize the coefficient of dynamic friction of the product, a machine comprising a carriage that moves over a distance of 100 mm on ball bearings may be used.

Correct movement of the carriage is ensured by means of a rigid connection with moving crosshead of a traction-compression machine (TAXT2 from the company Rheo) placed horizontally, with a magnet attached to the back of the carriage.

The product S whose coefficient of dynamic friction it is sought to evaluate is cut at one end with a tungsten wire of diameter 250 μm by removing the wire relative to the stick at a speed of 100 mm/minute and perpendicular to its longitudinal axis so as to have a flat contact surface parallel to the sliding surface W.

A normal force Fn is applied thereto at the sliding surface W by means of a weight. This weight is such that the pressure exerted on the surface of the product S in contact with W is 7.9×10³ MPa.

The product may be in the form of a circular cylindrical wand.

In the case where the cross section of the wand is not circular, the stick is slid in the direction of the small axis of its cross section, by moving the large axis parallel to itself.

The coefficient of friction is defined as the ratio of the tangential force Ft applied to the body moving in the direction M to the normal force Fn experienced by this same body, as illustrated in FIG. 15.

In a friction test, a first transient phase of start of movement of the system and a second phase of continuous regime may be distinguished.

In the first phase, the tangential force increases to reach a maximum that corresponds to the start of movement of the system. This maximum corresponds to the static friction force, known as the static Ft, and makes it possible to define a coefficient of static friction (μs)

μs=static Ft/Fn

where Fn is the applied normal force.

The tangential force Ft then decreases to generally reach a more stable regime. The coefficient of dynamic friction is defined in this phase of the movement as the ratio of the dynamic friction force (tangential force) to the applied normal force (Fn):

μd=dynamic Ft/Fn

The coefficient of friction is a dimensionless magnitude, which depends on the two surfaces in contact and on the contact conditions.

The sliding surface is defined by artificial skin of reference Bio Skin Plate Black K275 from the company Maprecos, with a width greater than or equal to the cross section of the stick.

For a measurement at 25° C., the apparatus and the composition are both at 25° C.

The artificial skin is placed on the support that may be heated to the temperature at which it is desired to measure the coefficient of dynamic friction. The wand initially at a temperature of 25° C. is applied, for example to the artificial skin thus heated, for example to 45° C. if the measurement is to be taken at 45° C. The surface temperature of the artificial skin may be monitored with an optical thermometer.

In certain embodiments, the coefficient of dynamic friction of a composition according to the invention is greater than or equal to 0.6, or even 0.7 or even 0.8 at 25° C. The coefficient of dynamic friction at 25° C. of the compositions according to the invention may be less than or equal to 5.

According to one particular embodiment, the stick may have a diameter of 12.7 mm in the region of its area of contact with the sliding surface, but other values are possible, for example ranging from 7 mm to 50 mm.

Hardness Measurement Protocol

The compositions under consideration according to the invention are relatively hard at room temperature and, under the action of heat, become soft enough to be able to be applied.

The hardness may be measured at 20° C. via the cheese wire method, which consists in transversely cutting a wand of product, which is preferably a circular cylinder, by means of a rigid tungsten wire 250 μm in diameter, by moving the wire relative to the stick at a speed of 100 mm/minute. The hardness corresponds to the maximum shear force exerted by the wire on the stick at 20° C., this force being measured using a DFGHS 2 tensile testing machine from the company Indelco-Chatillon. The measurement is repeated three times and then averaged.

The average of the three values read using the tensile testing machine mentioned above, noted Y, is given in grams. This average is converted into newtons and then divided by L which represents the longest distance through which the wire passes. In the case of a cylindrical wand, L is equal to the diameter in metres.

The hardness is converted by the equation below:

(Y×10⁻³×9.8)/L

For a measurement at a different temperature, the entire stick is heated to the temperature at which the hardness is to be measured.

According to this method, the hardness at 20° C. of examples of composition according to one aspect of the invention is greater than 80 Nm⁻¹, especially greater than 100 Nm⁻¹ and preferably greater than 120 Nm⁻¹.

Preferably, the composition according to the invention especially has a hardness at 20° C. of less than 500 Nm⁻¹, especially less than 400 Nm⁻¹ and preferably less than 300 Nm⁻¹.

A composition of the invention is cosmetically or dermatologically acceptable, i.e. it contains a non-toxic physiologically acceptable medium that can be applied to human lips. For the purposes of the invention, the term “cosmetically acceptable” refers to a composition of pleasant appearance, odour and feel that is suitable for use in cosmetics.

Polyesters

The composition according to the invention comprises at least one polyester.

A polyester that is suitable for use in the invention may advantageously be obtained by reacting a polyol, a polycarboxylic acid, a non-aromatic monocarboxylic acid and an aromatic monocarboxylic acid.

In particular, a polyester that is suitable for use in the invention may be preferentially obtained by reacting:

-   -   a tetraol containing from 4 to 10 carbon atoms;     -   a linear or branched saturated monocarboxylic acid containing         from 9 to 23 carbon atoms;     -   a cyclic dicarboxylic acid containing from 6 to 12 carbon atoms;     -   an aromatic monocarboxylic acid containing from 7 to 11 carbon         atoms.

Advantageously, a polyester of the invention may be obtained by reacting:

-   -   from 10% to 30% by weight of tetraol containing from 4 to 10         carbon atoms;     -   from 40% to 80% by weight of a linear or branched saturated         monocarboxylic acid containing from 9 to 23 carbon atoms;     -   from 5% to 30% by weight of a cyclic dicarboxylic acid         containing from 6 to 12 carbon atoms;     -   from 0.1% to 10% by weight of an aromatic monocarboxylic acid         containing from 7 to 11 carbon atoms,

the contents being expressed as weight percentages relative to the total weight of the polyester.

A polyester used according to the invention comprises a tetraol. The term “tetraol” means a polyol comprising 4 hydroxyl groups.

A tetraol used for the preparation of the polyester is advantageously a linear, branched and/or cyclic, saturated or unsaturated hydrocarbon-based compound containing from 4 to 10 carbon atoms, and possibly also comprising one or more oxygen atoms intercalated in the chain (ether function). Obviously, a mixture of such tetraols may be used.

A tetraol may in particular be a saturated, linear or branched hydrocarbon-based compound containing 4 to 10 carbon atoms.

A tetraol may be chosen from pentaerythritol or tetramethylolmethane, erythritol, diglycerol and ditrimethylolpropane.

Preferably, the tetraol is chosen from pentaerythritol and diglycerol.

Even more preferentially, a tetraol may be pentaerythritol.

The content of tetraol, or tetraol mixture, may represent from 10% to 30% by weight, especially from 12% to 25% by weight and better still from 14% to 22% by weight relative to the total weight of the polyester.

A polyester used according to the invention also comprises a linear or branched, saturated monocarboxylic acid containing from 9 to 23 carbon atoms and especially 12 to 22 carbon atoms.

The term “saturated monocarboxylic acid” means a compound of formula RCOOH in which R is a saturated linear or branched hydrocarbon-based radical containing from 8 to 22 carbon atoms and especially from 11 to 21 carbon atoms. Obviously, a mixture of such monocarboxylic acids may be used.

Among the saturated monocarboxylic acids that may be used, mention may be made, alone or as a mixture, of nonanoic acid, isononanoic acid or pelargonic acid, decanoic acid or capric acid, lauric acid, tridecanoic acid or tridecylic acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid and behenic acid.

Preferably, lauric acid, myristic acid, isononanoic acid, nonanoic acid, palmitic acid, isostearic acid, stearic acid or behenic acid, and mixtures thereof, may be used.

Preferentially, isostearic acid or stearic acid is used.

When the saturated monocarboxylic acid is liquid at room temperature, it generally leads to a polyester that is liquid at room temperature.

Liquid monocarboxylic acids that may be mentioned include nonanoic acid, isononanoic acid and isostearic acid.

When the saturated monocarboxylic acid is solid at room temperature, it generally leads to a polyester that is solid at room temperature.

Solid monocarboxylic acids that may be mentioned include decanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid.

The content of saturated monocarboxylic acid, or the mixture of the acids, represents from 40% to 80% by weight, especially from 42% to 75% by weight, or even 45% to 70% by weight and better still 50% to 65% by weight relative to the total weight of the polyester.

The polyester used according to the invention also comprises a cyclic dicarboxylic acid containing from 6 to 12 carbon atoms and especially containing 8 carbon atoms. The cyclic dicarboxylic acid may be aromatic or non-aromatic. The cyclic dicarboxylic acid is preferably aromatic.

Obviously, a mixture of such cyclic dicarboxylic acids may be used.

A cyclic dicarboxylic acid may be chosen from cyclopropanedicarboxylic acid, cyclohexanedicarboxylic acid, cyclobutanedicarboxylic acid, phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic acid, naphthalene-2,3-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid, or mixtures thereof.

Preferably, the cyclic dicarboxylic acid is chosen from phthalic acid, terephthalic acid and isophthalic acid. Phthalic acid may be advantageously used in its anhydride form.

Preferentially, the cyclic dicarboxylic acid is isophthalic acid.

A cyclic dicarboxylic acid, or a mixture of such diacids, may represent from 5% to 30% by weight and preferably from 15% to 25% by weight relative to the total weight of the polyester.

A polyester used according to the invention also comprises an aromatic monocarboxylic acid containing from 7 to 11 carbon atoms.

The term “aromatic monocarboxylic acid” means a compound of formula R′COOH, in which R′ is an aromatic hydrocarbon-based radical containing 6 to 10 carbon atoms; R′ is in particular a phenyl radical, optionally substituted with 1 to 3 alkyl radicals containing from 1 to 4 carbon atoms.

Obviously, a mixture of such aromatic monocarboxylic acids may be used.

The aromatic monocarboxylic acid may be chosen from benzoic acid and 4-tert-butylbenzoic acid.

The aromatic monocarboxylic acid is preferably benzoic acid.

The aromatic monocarboxylic acid, or the mixture of the acids, represents from 0.1% to 10% by weight, especially from 0.5% to 9.95% by weight and better still from 1% to 9.5% by weight, or even from 1.5% to 8% by weight relative to the total weight of the polyester.

According to one preferred embodiment, the polyester is obtained by reacting:

-   -   from 12% to 25% by weight of a tetraol containing from 4 to 10         carbon atoms;     -   from 40% to 75% by weight of a linear or branched saturated         monocarboxylic acid containing from 9 to 23 carbon atoms;     -   from 15% to 25% by weight of a cyclic dicarboxylic acid         containing from 6 to 12 carbon atoms;     -   from 0.5% to 9.95% by weight of an aromatic monocarboxylic acid         containing from 7 to 11 carbon atoms,

the contents being expressed as weight percentages relative to the total weight of the polyester.

According to another preferred embodiment, the polyester is obtained by reacting:

-   -   from 14% to 22% by weight of a tetraol containing from 4 to 10         carbon atoms;     -   from 45% to 70% by weight of a linear or branched saturated         monocarboxylic acid containing from 9 to 23 carbon atoms;     -   from 15% to 25% by weight of a cyclic dicarboxylic acid         containing from 6 to 12 carbon atoms;     -   from 1% to 9.5% by weight of an aromatic monocarboxylic acid         containing from 7 to 11 carbon atoms,

the contents being expressed as weight percentages relative to the total weight of the polyester.

According to another preferred embodiment, the polyester is obtained by reacting:

-   -   from 14% to 22% by weight of a tetraol containing from 4 to 10         carbon atoms;     -   from 50% to 65% by weight of a linear or branched, saturated         monocarboxylic acid containing from 9 to 23 carbon atoms;     -   from 15% to 25% by weight of a cyclic dicarboxylic acid         containing from 6 to 12 carbon atoms;     -   from 1.5% to 8% by weight of an aromatic monocarboxylic acid         containing from 7 to 11 carbon atoms,

the contents being expressed as weight percentages relative to the total weight of the polyester.

In one preferred embodiment of the polyester used according to the invention, the aromatic monocarboxylic acid is present in a molar amount of less than or equal to that of the linear or branched saturated monocarboxylic acid; in particular, the ratio between the number of moles of aromatic monocarboxylic acid and the number of moles of linear or branched saturated monocarboxylic acid ranges from 0.08 to 0.70. The weight ratio preferably ranges between 0.10 and 0.60 and more preferentially from 0.12 to 0.40.

According to one embodiment of the invention, a polyester of the invention may be chosen from benzoic acid/isophthalic acid/isostearic acid/pentaerythritol polyesters and benzoic acid/isophthalic acid/stearic acid/pentaerythritol polyesters, and mixtures thereof.

These monomers are especially used in the monomer concentration ranges described previously.

Preferably, the polyester has:

-   -   an acid number, expressed as mg of potassium hydroxide per g of         polyester, of greater than or equal to 1; especially between 2         and 30 and even better still between 2.5 and 15; and/or     -   a hydroxyl number, expressed in mg of potassium hydroxide per g         of polyester, of greater than or equal to 40; especially between         40 and 120 and better still between 40 and 80.

These acid and hydroxyl numbers may be readily determined by a person skilled in the art via the usual analytical methods.

Preferably, a polyester of the invention has a weight-average molecular mass (Mw) of between 3000 and 1 000 000 g/mol, or even between 3000 and 300 000 g/mol.

The average molecular weight may be determined by gel permeation chromatography or by light scattering, depending on the solubility of the polymer under consideration.

Preferably, a polyester of the invention has a viscosity, measured at 110° C., of between 20 and 4000 mPa·s, especially between 30 and 3500 mPa·s or even between 40 and 3000 mPa·s and better still between and 2500 mPa·s. This viscosity is measured in the manner described hereinbelow.

According to one preferred embodiment, the polyester may be in liquid form at room temperature. A liquid polyester may have a weight-average molecular mass (Mw) ranging from 40 000 to 1 000 000 g/mol and preferably ranging from 50 000 to 300 000 g/mol.

A liquid polyester may have a viscosity, measured at 110° C., ranging from 1000 to 4000 mPa·s and preferably ranging from 1500 to 3000 mPa·s.

In particular, a liquid polyester may be a benzoic acid/isophthalic acid/isostearic acid/pentaerythritol polyester, these monomers especially being present in the monomer concentration ranges described previously.

According to another embodiment, the polyester may also be in solid form at room temperature. A solid polyester may have a weight-average molecular mass (Mw) ranging from 3000 to 30 000 g/mol and preferably ranging from 8000 to 15 000 g/mol.

The solid polyester may have a viscosity, measured at 80° C., ranging from 20 to 1000 mPa·s and preferably ranging from 50 to 600 mPa·s.

In particular, a solid polyester may be a benzoic acid/isophthalic acid/stearic acid/pentaerythritol polyester, these monomers being present especially in the monomer concentration ranges described previously.

A polyester of the invention may be prepared according to the synthetic process described in patent application EP-A-1 870 082.

The viscosity of a polyester of the invention may be measured in the manner described hereinbelow.

The viscosity at 80° C. or at 110° C. of a polyester is measured using a cone-plate viscometer of Brookfield CAP 1000+ type.

The appropriate cone-plate is determined by a person skilled in the art on the basis of his knowledge; especially:

-   -   between 50 and 500 mPa·s, a 03 cone may be used,     -   between 500 and 1000 mPa·s: 03 cone,     -   between 1000 and 4000 mPa·s: 05 cone, and     -   between 4000 and 10 000 mPa·s: 06 cone.

The amount of polyester present in a composition of the invention may range from 1% to 60% by weight, preferably from 2% to 50% by weight, especially from 3% to 45% by weight, or even from 4% to 35% by weight and better still from 5% to 30% by weight relative to the total weight of the composition.

A polyester that is suitable for use in the invention may be readily conveyed in cosmetic oily or solvent media, especially oils, fatty alcohols and/or fatty esters.

A polyester of the invention may be readily prepared, in a single synthetic step, without producing any waste, and at low cost.

A polyester that is suitable for use in the invention may advantageously be branched so as to generate a network by interweaving of polymer chains, and thus to obtain the desired properties, especially in terms of improved remanence and improved gloss, and in terms of solubility.

According to one embodiment, a composition of the invention may comprise at least two polyesters that are different from each other.

Preferably, the polyester is present in a composition according to the invention in a content ranging from 1% to 60% by weight, preferably from 5% to 50% by weight, especially from 10% to 45% by weight, or even from 10% to 35% by weight and better still from 15% to 30% by weight relative to the total weight of the composition.

Fatty Phase

Solid Fatty Substance:

The composition according to the invention comprises at least one solid fatty substance chosen from waxes and pasty fatty substances, and a mixture thereof.

Wax

The wax under consideration in the context of the present invention is generally a lipophilic compound that is solid at room temperature (25° C.), with a solid/liquid reversible change of state, having a melting point of greater than or equal to 30° C., which may be up to 200° C. and in particular up to 120° C.

According to one embodiment of the invention, hair-removing waxes are excluded, as waxes that are suitable for use in the invention.

In particular, the waxes that are suitable for the invention may have a melting point of greater than or equal to 45° C. and in particular greater than or equal to 55° C.

For the purposes of the invention, the melting point corresponds to the temperature of the most endothermic peak observed by thermal analysis (DSC) as described in ISO standard 11357-3; 1999. The melting point of the wax may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name “MDSC 2920” by the company TA Instruments.

The measuring protocol is as follows:

A sample of 5 mg of wax placed in a crucible is subjected to a first temperature rise ranging from −20° C. to 100° C., at a heating rate of 10° C./minute, it is then cooled from 100° C. to −20° C. at a cooling rate of 10° C./minute and is finally subjected to a second temperature increase ranging from −20° C. to 100° C. at a heating rate of 5° C./minute. During the second temperature increase, the variation of the difference in power absorbed by the empty crucible and by the crucible containing the sample of wax is measured as a function of the temperature. The melting point of the compound is the temperature value corresponding to the top of the peak of the curve representing the variation in the difference in absorbed power as a function of the temperature.

The waxes that may be used in the compositions according to the invention are chosen from waxes that are solid at room temperature, of animal, plant, mineral or synthetic origin, and mixtures thereof.

As illustrations of waxes that are suitable for use in the invention, mention may be made especially of hydrocarbon-based waxes, for instance beeswax, lanolin wax and Chinese insect waxes, rice bran wax, carnauba wax, candelilla wax, ouricury wax, alfalfa wax, berry wax, shellac wax, Japan wax and sumach wax; montan wax, orange wax and lemon wax, microcrystalline waxes (such as the wax sold under the reference Microwax HW by the company Paramelt), paraffins and ozokerite; polyethylene waxes such as those sold under the name Performalene 500-L and Performalene 400 by the company New Phase Technologies, and the waxes obtained by Fisher-Tropsch synthesis.

Mention may also be made of the waxes obtained by catalytic hydrogenation of animal or plant oils with linear or branched C₈-C₃₂ fatty chains. Among these, mention may be made especially of isomerized jojoba oil such as the trans-isomerized partially hydrogenated jojoba oil manufactured or sold by the company Desert Whale under the trade reference Iso-Jojoba-50®, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated lanolin oil, and the bis(1,1,1-trimethylolpropane) tetrastearate sold under the name Hest 2T-4S® by the company Heterene.

Mention may also be made of silicone waxes (C₃₀₋₄₅ Alkyl Dimethicone) and fluoro waxes.

It is also possible to use the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol, sold under the names Phytowax Ricin 16L64® and 22L73® by the company Sophim. Such waxes are described in patent application FR-A-2 792 190.

It is possible to use a C₂₀-C₄₀ alkyl (hydroxystearyloxy)stearate (the alkyl group comprising from 20 to 40 carbon atoms) as wax, alone or as a mixture. Such a wax is sold especially under the names Kester Wax K 82 P®, Hydroxypolyester K 82 P®, Kester Wax K 80 P® and Kester Wax K 82 H® by the company Koster Keunen.

As microwaxes that may be used in the compositions according to the invention, mention may be made especially of carnauba microwaxes such as the product sold under the name MicroCare 350® by the company Micro Powders, synthetic microwaxes such as the product sold under the name MicroEase 114S® by the company Micro

Powders, microwaxes formed from a mixture of carnauba wax and polyethylene wax, such as those sold under the names MicroCare 300® and 310® by the company Micro Powders, microwaxes formed from a mixture of carnauba wax and synthetic wax, such as the product sold under the name MicroCare 325® by the company Micro Powders, polyethylene microwaxes such as those sold under the names Micropoly 200®, 220®, 220L® and 250S® by the company Micro Powders, and polytetrafluoroethylene microwaxes such as those sold under the names Microslip 519® and 519 L® by the company Micro Powders.

The composition according to the invention may comprise a content of waxes ranging from 0.1% to 50% by weight, in particular from 0.1% to 45% by weight, for example from 2% to 35% by weight, 4% to 30% by weight or, according to certain embodiments, from 4% to 15% by weight, relative to the total weight of the composition.

Pasty Compounds

The composition according to the invention may also comprise at least one pasty compound.

For the purposes of the present invention, the term “pasty compound” is intended to denote a lipophilic fatty compound that undergoes a reversible solid/liquid change of state, that has anisotropic crystal organization in the solid state, and that comprises, at a temperature of 23° C., a liquid fraction and a solid fraction.

In other words, the starting melting point of the pasty compound is less than 23° C. The liquid fraction of the pasty compound measured at 23° C. may represent 9% to 97% by weight of the compound. This liquid fraction at 23° C. preferably represents between 15% and 85% and more preferably between 40% and 85% by weight.

The liquid fraction by weight of the pasty compound at 23° C. is equal to the ratio of the heat of fusion consumed at 23° C. to the heat of fusion of the pasty compound.

The heat of fusion of the pasty compound is the heat consumed by the compound to change from the solid state to the liquid state. The pasty compound is said to be in the solid state when all of its mass is in solid form. The pasty compound is said to be in the liquid state when all of its mass is in liquid form.

The heat of fusion of the pasty compound is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DSC), such as the calorimeter sold under the name MDSC 2920 by the company TA Instruments, with a temperature rise of 5 or 10° C. per minute, according to standard ISO 11357-3:1999. The heat of fusion of the pasty compound is the amount of energy required to make the compound change from the solid state to the liquid state. It is expressed in J/g.

The heat of fusion consumed at 23° C. is the amount of energy absorbed by the sample to change from the solid state to the state that it has at 23° C., consisting of a liquid fraction and a solid fraction.

The liquid fraction of the pasty compound, measured at 32° C., preferably represents from 30% to 100% by weight of the compound, preferably from 50% to 100% and more preferably from 60% to 100% by weight of the compound. When the liquid fraction of the pasty compound measured at 32° C. is equal to 100%, the temperature of the end of the melting range of the pasty compound is less than or equal to 32° C.

The liquid fraction of the pasty compound measured at 32° C. is equal to the ratio of the heat of fusion consumed at 32° C. to the heat of fusion of the pasty compound. The heat of fusion consumed at 32° C. is calculated in the same manner as the heat of fusion consumed at 23° C.

The pasty compound is preferably chosen from synthetic compounds and compounds of plant origin. A pasty compound may be obtained by synthesis starting from starting materials of plant origin.

The pasty compound may be advantageously chosen from:

-   -   i) lanolin and derivatives thereof,     -   ii) polymeric or non-polymeric silicone compounds,     -   iii) polymeric or non-polymeric fluoro compounds,     -   iv) vinyl polymers, especially:         -   olefin homopolymers and olefin copolymers,         -   hydrogenated diene homopolymers and copolymers,         -   linear or branched oligomers, which are homopolymers or             copolymers of alkyl (meth)acrylates preferably containing a             C₈-C₃₀ alkyl group,         -   vinylpyrrolidone/eicosene copolymers (INCI name VP/eicosene             copolymer), for example the product sold by the company ISP             under the trade name Ganex V220F®,         -   oligomers, which are homopolymers and copolymers of vinyl             ethers containing C₈-C₃₀ alkyl groups,     -   v) liposoluble polyethers resulting from polyetherification         between one or more C₂-C₁₀₀ and preferably C₂-C₅₀ diols,     -   vi) esters,     -   vii) and mixtures thereof.

Among the esters, the following are especially preferred:

-   -   esters of a glycerol oligomer, especially diglycerol esters, in         particular condensates of adipic acid and of glycerol, for which         some of the hydroxyl groups of the glycerols have reacted with a         mixture of fatty acids such as stearic acid, capric acid,         stearic acid and isostearic acid, and 12-hydroxystearic acid,         especially such as bis(diglyceryl) poly(2-acyladipate),         especially the product sold under the brand name Softisan 649®         by the company Sasol,     -   arachidyl propionate sold under the brand name Waxenol 801 by         Alzo,     -   phytosterol esters,     -   fatty acid triglycerides and derivatives thereof,     -   pentaerythritol esters,     -   non-crosslinked polyesters resulting from polycondensation         between a linear or branched C₄-C₅₀ dicarboxylic acid or         polycarboxylic acid and a C₂-C₅₀ diol or polyol,     -   aliphatic esters of an ester resulting from the esterification         of an aliphatic hydroxycarboxylic acid ester with an aliphatic         carboxylic acid,     -   esters resulting from the esterification of an aliphatic acid         and a hydroxylated aliphatic ester. These esters may result from         the esterification a) of a monocarboxylic or polycarboxylic         aliphatic acid, and b) of a hydroxylated aliphatic ester,         especially a hydroxycarboxylic acid ester,     -   esters of diol dimer and of diacid dimer, where appropriate         esterified on their free alcohol or acid function(s) with acid         or alcohol radicals, such as bisbehenyl/isostearyl/phytosteryl         dimer dilinoleyl sold especially under the trade name         Plandool-G® by the company Nippon Fine Chemical,     -   and mixtures thereof.

Among the pasty compounds, bis-behenyl/isostearyl/phytosteryl dimer dilinoleyl, bis(diglyceryl) poly(2-acyladipate), hydrogenated castor oil dimer dilinoleate, for example Risocast DA-L sold by Kokyu Alcohol Kogyo, and hydrogenated castor oil isostearate, for example Salacos HCIS (V-L) sold by Nisshin Oil, or a mixture thereof, will preferably be chosen.

The content of pasty compound may range from 5% to 90% by weight, especially from 5% to 50% by weight, or even, in certain embodiments, from 5% to 35% by weight, relative to the total weight of the composition.

Oil

According to one preferred embodiment, the composition according to the invention comprises at least one oil.

The term “oil” means a non-aqueous compound, which is liquid at room temperature (25° C.) and atmospheric pressure (760 mmHg).

The oil may be volatile or non-volatile.

For the purposes of the invention, a volatile oil has, at room temperature (25° C.) and atmospheric pressure (760 mmHg), a vapour pressure ranging from 0.02 mmHg to 300 mmHg (2.66 Pa to 40 000 Pa) and better still ranging from 0.1 to 90 mmHg (13 Pa to 12 000 Pa).

Non-volatile oils then correspond to a vapour pressure below 0.02 mmHg (2.66 Pa) and better still below 10⁻³ mmHg (0.13 Pa).

The volatile oil may be a silicone oil, a hydrocarbon-based oil or a fluoro oil.

According to a first variant, the volatile oil may be a volatile silicone oil.

The term “silicone oil” means an oil comprising at least one silicon atom, especially comprising Si—O groups.

The volatile silicone oil that may be used in the invention may be chosen from silicone oils with a flash point ranging from 40° C. to 150° C., preferably with a flash point of greater than 55° C. and less than or equal to 105° C., and preferentially ranging from 65° C. to 95° C. The flash point is measured in particular according to standard ISO 3679.

The volatile silicone oil may be chosen from linear or cyclic silicone oils such as linear or cyclic polydimethylsiloxanes (PDMS) containing from 3 to 7 silicon atoms.

Examples of such oils that may be mentioned include octyl trimethicone, hexyl trimethicone, decamethylcyclopentasiloxane (cyclopentasiloxane or D5), octamethylcyclotetrasiloxane (cyclotetradimethylsiloxane or D4), dodecamethylcyclohexasiloxane (D6), decamethyltetrasiloxane (L4), KF 96 A from Shin-Etsu, and polydimethylsiloxanes such as those sold under the references DC 200 (1.5 cSt), DC 200 (5 cSt) and DC 200 (3 cSt) by Dow Corning.

According to another variant, the volatile oil may be a volatile hydrocarbon-based oil.

The term “hydrocarbon-based oil” means an oil formed essentially from, or even constituted by, carbon and hydrogen atoms, and optionally oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.

The volatile hydrocarbon-based oils (also known as solvents) may be chosen from hydrocarbon-based oils containing from 8 to 16 carbon atoms, especially branched C8-C16 alkanes such as C8-C16 isoalkanes of petroleum origin (also known as isoparaffins), for instance isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane and, for example, the oils sold under the trade names Isopar and Permethyl, branched C8-C16 esters and isohexyl neopentanoate, and mixtures thereof. Other volatile hydrocarbon-based oils, for instance petroleum distillates, especially those sold under the name Shell Solt by the company Shell, may also be used. Preferably, the volatile solvent is chosen from volatile hydrocarbon-based oils containing from 8 to 16 carbon atoms, and mixtures thereof.

As other volatile hydrocarbon-based solvents (oils) that may be used in the composition according to the invention, mention may also be made of ketones that are liquid at room temperature, such as methyl ethyl ketone or acetone; short-chain esters (containing from to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate; ethers that are liquid at room temperature, such as diethyl ether, dimethyl ether or dichlorodiethyl ether; alcohols and especially linear or branched lower monoalcohols containing from 2 to 5 carbon atoms, such as ethanol, isopropanol or n-propanol.

According to one preferred embodiment, the composition used according to the invention comprises a content of volatile oil of less than 5% by weight, preferably ranging from 0% to 30% by weight relative to the total weight of the composition, or alternatively is free of volatile oil.

According to one preferred embodiment, the composition used according to the invention is free of volatile oil.

Non-volatile oil

According to one preferred embodiment, the composition used according to the invention comprises at least one non-volatile oil.

The term “non-volatile oil” means an oil that remains on keratin materials at room temperature and atmospheric pressure for at least several hours and that especially has a vapour pressure of less than 10⁻³ mmHg (0.13 Pa). A non-volatile oil may also be defined as having an evaporation rate such that, under the conditions defined previously, the amount evaporated after 30 minutes is less than 0.07 mg/cm².

The non-volatile oil may be a hydrocarbon-based oil, a silicone oil or a fluoro oil.

Preferably, the composition according to the invention comprises a content of non-volatile oil ranging from 1% to 90% by weight, preferably from 5% to 80% by weight, better still from 10% to 75% by weight, better still from 20% to 70% by weight and even better still from 30% to 70% by weight relative to the total weight of the composition.

According to a first embodiment, the composition used in the invention comprises at least one non-volatile oil with a molar mass of less than 500 g/mol.

These oils may be of plant, mineral or synthetic origin.

As examples of non-volatile oils that may be used in the invention, mention may be made of:

-   -   hydrocarbon-based plant oils such as liquid triglycerides of         fatty acids containing from 4 to 10 carbon atoms, for instance         heptanoic or octanoic acid triglycerides; jojoba oil or         squalane;     -   fatty alcohols containing from 12 to 26 carbon atoms, for         instance octyldodecanol, 2-butyloctanol, 2-hexyldecanol,         2-undecylpentadecanol or oleyl alcohol;     -   ester oils such as:         -   fatty acid esters, in particular of 4 to 22 carbon atoms,             and especially of octanoic acid, heptanoic acid, lanolic             acid, oleic acid, lauric acid or stearic acid, for instance             propylene glycol dioctanoate, propylene glycol             monoisostearate or neopentyl glycol diheptanoate,         -   synthetic esters, for instance the oils of formula R₁COOR₂             in which R₁ represents a linear or branched fatty acid             residue comprising from 4 to 25 carbon atoms and R₂             represents a hydrocarbon-based chain, which is especially             branched, containing from 4 to 25 carbon atoms, on condition             that R₁+R₂ (i.e. the sum of the carbon atoms of R₁ and of             R₂) is between 16 and 30, for instance Purcellin oil             (cetostearyl octanoate), isononyl isononanoate, C₁₂ to C₁₅             alkyl benzoates, 2-ethylhexyl palmitate, octyldodecyl             neopentanoate, 2-octyldodecyl stearate, 2-octyldodecyl             erucate, isostearyl isostearate, 2-octyldodecyl benzoate,             alcohol or polyalcohol octanoates, decanoates or             ricinoleates, isopropyl myristate, isopropyl palmitate,             butyl stearate, hexyl laurate, 2-ethylhexyl palmitate,             2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl             myristate or 2-diethylhexyl succinate;         -   hydroxylated esters, for instance isostearyl lactate, octyl             hydroxystearate, octyldodecyl hydroxystearate or glyceryl             stearate; diethylene glycol diisononanoate; and     -   silicone oils with a molecular weight of less than 500 g/mol,         for instance linear or cyclic polydimethylsiloxanes (PDMS);         polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups,         which are pendent or at the end of a silicone chain, these         groups containing from 2 to 24 carbon atoms;     -   fatty acids containing from 12 to 26 carbon atoms, for instance         oleic acid;     -   and mixtures thereof.

According to a first embodiment, the composition used according to the invention is free of oil with a molecular weight of less than 500 g/mol.

According to another embodiment, the composition used according to the invention comprises a content of non-volatile oil with a molecular weight of less than 500 g/mol ranging from 0.1% to 80% by weight, preferably from 0.1% to 60% by weight, better still from 0.1% to 50% by weight and even better still from 1% to 40% by weight relative to the total weight of the composition.

Glossy Oil

Preferably, the composition according to the invention comprises at least one non-volatile oil with a molecular weight of greater than 500 g/mol, known as a “glossy oil”.

The glossy oil preferably has a high molar mass, i.e. ranging from 500 to 100 000 g/mol, preferably ranging from 500 to 25 000 g/mol or alternatively from 500 to 10 000 g/mol.

Preferably, the glossy oil has a refractive index of greater than or equal to 1.45 and especially ranging from 1.45 to 1.65.

The glossy oil that may be used in the present invention may be chosen from:

-   -   lipophilic polymers such as:         -   polybutylenes such as Indopol H-100 (of molar mass MW=965             g/mol), Indopol H-300 (MW=1340 g/mol) or Indopol H-1500             (MW=2160 g/mol) sold or manufactured by the company Amoco,         -   hydrogenated polyisobutylenes such as Panalane H-300 E sold             or manufactured by Amoco (MW=1340 g/mol), Viseal 20000 sold             or manufactured by the company Synteal (MW=6000 g/mol) and             Rewopal PIB 1000 sold or manufactured by the company Witco             (MW=1000 g/mol),         -   polydecenes and hydrogenated polydecenes such as: Puresyn 10             (MW=723 g/mol) and Puresyn 150 (MW=9200 g/mol) sold or             manufactured by the company Mobil Chemicals,         -   vinylpyrrolidone copolymers such as: the             vinylpyrrolidone/1-hexadecene copolymer Antaron V-216 sold             or manufactured by the company ISP (MW=7300 g/mol),     -   esters such as:         -   pentaerythritol esters;         -   esters of aromatic acids and of alcohols comprising 4 to 22             carbon atoms, especially tridecyl trimellitate;         -   hydroxylated esters such as diisostearyl malate or             polyglyceryl-2 triisostearate (MW=965 g/mol), aromatic             esters such as tridecyl trimellitate (MW=757 g/mol),         -   C₂₄-C₂₈ esters of branched fatty alcohols or fatty acids             such as those described in patent application EP-A-0 955             039, and especially triisoarachidyl citrate (MW=1033.76             g/mol), pentaerythrityl tetraisononanoate (MW=697 g/mol),             glyceryl triisostearate (MM=891 g/mol), glyceryl             tris(2-decyl)tetradecanoate (MW=1143 g/mol), pentaerythrityl             tetraisostearate (MW=1202 g/mol), polyglyceryl-2             tetraisostearate (MW=1232 g/mol) or pentaerythrityl             tetrakis(2-decyl)tetradecanoate (MW=1538 g/mol),         -   esters of a diol dimer and of a diacid dimer of general             formula:

HO—R¹—(—OCO—R²—COO—R¹—)_(h)—OH

-   -   -   in which:

    -   R¹ represents a diol dimer obtained by hydrogenation of         dilinoleic diacid,

    -   R² represents a hydrogenated dilinoleic diacid residue, and

    -   h represents an integer ranging from 1 to 9,

    -   especially the esters of dilinoleic diacids and of dilinoleyl         diol dimers sold by the company Nippon Fine Chemical under the         trade names Lusplan DD-DA5® and DD-DA7®,

    -   silicone oils such as phenyl silicones, and

    -   mixtures thereof.

Preferably, when the glossy oil is a hydrocarbon-based oil, it preferably has a molar mass ranging from 500 to 10 000 g/mol and preferably from 500 to 7500 g/mol.

Preferably, the glossy oil has a refractive index of greater than or equal to 1.45, especially ranging from 1.45 to 1.65.

Preferably, the oil with a molecular weight of greater than 500 g/mol may represent from 1% to 90% by weight, preferably from 5% to 80% by weight, better still from 10% to 75% by weight, better still from 20% to 70% by weight and even better still from 30% to 70% by weight relative to the total weight of the composition.

According to one preferred embodiment, the composition according to the invention comprises at least one non-volatile phenyl silicone oil (also known as a “phenyl silicone”).

In particular, the composition according to the invention preferably comprises at least one phenyl silicone oil with a molecular weight of greater than 500 g/mol (known as a “glossy oil”). Preferably, the weight-average molecular weight of the phenyl silicone oil is between 500 and 10 000 g/mol and preferably between 500 and 7500 g/mol.

The term “phenyl silicone oil” means an organopolysiloxane substituted with at least one phenyl group.

The silicone oil may be chosen from phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes and 2-phenylethyl trimethylsiloxysilicates.

The silicone oil may correspond to the formula:

in which the groups R represent, independently of each other, a methyl or a phenyl. Preferably, in this formula, the silicone oil comprises at least three phenyl groups, for example at least four, at least five or at least six.

According to one preferred embodiment of the invention, the silicone oil corresponds to formula A1:

in which the groups R represent, independently of each other, a methyl or a phenyl. Preferably, in this formula, the organopolysiloxane comprises at least three phenyl groups, for example at least four or at least five.

Mixtures of the phenyl organopolysiloxanes described previously may be used.

Examples that may be mentioned include mixtures of tetraphenyl or pentaphenyl organopolysiloxanes.

According to this embodiment, the silicone oil preferably corresponds to the formula:

in which Me represents a methyl group and Ph represents a phenyl group. Such a phenyl silicone is especially manufactured by Dow Corning under the reference Dow Corning 555 Cosmetic Fluid (INCI name: trimethyl pentaphenyl trisiloxane). The reference Dow Corning 554 Cosmetic Fluid may also be used.

According to another embodiment, the silicone oil corresponds to the formula:

in which Me represents a methyl group, y is between 1 and 1000 and X represents —CH₂—CH(CH₃)(Ph).

According to another embodiment, the silicone oil corresponds to the formula:

in which —OR′ represents a group —O—SiMe₃, y is between 1 and 1000 and z is between 1 and 1000.

The phenyl silicone oil may be chosen from the phenyl silicones of formula (VI) below:

in which

-   -   R₁ to R₁₀, independently of each other, are saturated or         unsaturated, linear, cyclic or branched C1-C30 hydrocarbon-based         radicals,     -   m, n, p and q are, independently of each other, integers between         0 and 900, with the proviso that the sum m+n+q is other than 0.

Preferably, the sum m+n+q is between 1 and 100. Preferably, the sum m+n+p+q is between 1 and 900, and better still between 1 and 800. Preferably, q is equal to 0.

The phenyl silicone oil may be chosen from the phenyl silicones of formula (VII) below:

in which:

-   -   R1 to R6, independently of each other, are saturated or         unsaturated, linear, cyclic or branched C1-C30 hydrocarbon-based         radicals,     -   m, n and p are, independently of each other, integers between 0         and 100, with the proviso that the sum n+m is between 1 and 100.

Preferably, R1 to R6, independently of each other, represent a saturated, linear or branched C1-C30 and especially C1-C12 hydrocarbon-based radical and in particular a methyl, ethyl, propyl or butyl radical.

R1 to R6 may especially be identical, and in addition may be a methyl radical.

Preferably, m=1 or 2 or 3, and/or n=0 and/or p=0 or 1 may apply, in formula (VII).

A phenyl silicone oil of formula (VI) with a viscosity at 25° C. of between 5 and 1500 mm²/s (i.e. 5 to 1500 cSt), and preferably with a viscosity of between 5 and 1000 mm²/s (i.e. 5 to 1000 cSt) may be used.

As phenyl silicone oil of formula (VII), it is especially possible to use phenyl trimethicones such as Belsil oils, especially Belsil PDM1000 (1000 cSt) and Belsil PDM 200 (200 cSt) from Wacker, the oil Silbione 70663V30 from Rhône-Poulenc (28 cSt) or diphenyl dimethicones. The values in parentheses represent the viscosities at 25° C.

The non-volatile silicone oil may be chosen from the silicones of formula:

in which:

R₁, R₂, R₅ and R₆ are, together or separately, an alkyl radical containing 1 to 6 carbon atoms,

R₃ and R₄ are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms or an aryl radical,

X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical or a vinyl radical,

n and p being chosen so as to give the oil a weight-average molecular mass of less than 200 000 g/mol, preferably less than 150 000 g/mol and more preferably less than 100 000 g/mol.

In particular, phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenyl siloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxane, trimethyl pentaphenyl trisiloxane (especially 1,3,5-trimethyl-1,1,3,5,5-pentaphenyltrisiloxane sold under the name PH-1555 HRI by Dow Corning), and mixtures thereof, are preferably used as phenyl silicone oil.

Preferably, the phenyl silicone oil with a molecular weight of greater than 500 g/mol (such as an oil of formula A1) is present in a content ranging from 1% to 90% by weight, preferably from 5% to 80% by weight, better still from 10% to 75% by weight, better still from 20% to 70% by weight and even better still from 30% to 70% by weight relative to the total weight of the composition.

Preferably, when the composition comprises a phenyl silicone oil, it is present in the composition in a phenyl silicone oil/polyester weight ratio of between 1 and 20 and preferably between 1.5 and 10.

Preferably, the composition comprises a phenyl silicone oil with a molecular weight of greater than 500 g/mol and at least one hydrocarbon-based oil with a molecular weight of greater than 500 g/mol.

Besides the abovementioned compounds, a composition according to the invention may also comprise other compounds especially as defined hereinbelow. It is understood that the amount of these additional compounds may be adjusted by a person skilled in the art so as not to adversely affect the desired effect in the context of the present invention.

In particular, according to one preferred embodiment, the composition used according to the invention comprises at least one additional ingredient chosen from dyestuffs, fillers, non-volatile oils, structuring agents other than waxes or pasty fatty substances, semi-crystalline polymers, film-forming polymers and silicone polyamides.

Other Structuring Agents

The composition according to the present invention may also comprise additional structuring agents other than a wax as defined previously. The term “structuring agent” means a compound that is capable of increasing the viscosity of the composition into which it is incorporated. The additional structuring agent makes it possible especially to obtain a composition that may have a texture ranging from fluid to solid textures.

In this respect, mention may be made especially of:

-   -   organophilic clays, for instance hectorites modified with a C₁₀         to C₂₂ ammonium chloride, for instance hectorite modified with         distearyldimethylammonium chloride, for instance the product         sold under the name Bentone 38V® by the company Elementis;     -   fumed silicas, for instance fumed silicas optionally         hydrophobically surface-treated, the particle size of which is         less than 1 μm. The reason for this is that it is possible to         chemically modify the surface of silica, by chemical reaction         generating a decrease in the number of silanol groups present at         the surface of silica. It is especially possible to substitute         silanol groups with hydrophobic groups: a hydrophobic silica is         then obtained. The hydrophobic groups may be:     -   1. trimethylsiloxyl groups, which are especially obtained by         treating fumed silica in the presence of hexamethyldisilazane.         Silicas thus treated are known as “Silica silylate” according to         the CTFA (8th edition, 2000). They are sold, for example, under         the references Aerosil R812® by the company Degussa, and         Cab-O-Sil TS-530® by the company Cabot,     -   2. dimethylsilyloxyl or polydimethylsiloxane groups, which are         especially obtained by treating fumed silica in the presence of         polydimethylsiloxane or dimethyldichlorosilane. Silicas thus         treated are known as “Silica dimethyl silylate” according to the         CTFA (8th edition, 2000). They are sold, for example, under the         references Aerosil R972® and Aerosil R974® by the company         Degussa, and Cab-O-Sil TS-610® and Cab-O-Sil TS-720® by the         company Cabot.     -   alkyl guar gums (with a C1-C6 alkyl group), such as those         described in EP-A-708 114, or, for example, cellulose         derivatives such as ethylcellulose, for instance the product         sold under the name Ethocel® by the company Dow Chemical;     -   hydrocarbon-based block copolymers, also known as block         copolymers, preferably a block copolymer that is soluble or         dispersible in a liquid fatty phase.

The hydrocarbon-based block copolymer may especially be a diblock, triblock, multiblock, radial or star copolymer, or mixtures thereof.

Such hydrocarbon-based block copolymers are described in patent application US-A-2002/005 562 and in U.S. Pat. No. 5,221,534.

Diblock copolymers, which are preferably hydrogenated, that may be mentioned include styrene-ethylene/propylene copolymers, styrene-ethylene/butadiene copolymers and styrene-ethylene/butylene copolymers. The diblock polymers are especially sold under the name Kraton® G1701E by the company Kraton Polymers.

Triblock copolymers, which are preferably hydrogenated, that may be mentioned include styrene-ethylene/propylene-styrene copolymers, styrene-ethylene/butadiene-styrene copolymers, styrene-ethylene/butylene-styrene copolymers, styrene-isoprene-styrene copolymers and styrene-butadiene-styrene copolymers. Triblock copolymers are especially sold under the names Kraton® G1650, Kraton® G1652, Kraton® D1101, Kraton® D1102 and Kraton® D1160 by the company Kraton Polymers.

-   -   and mixtures thereof.

Such other structuring agents may be included in the composition in accordance with the invention in a content of between 0.5% and 20% by weight and especially between 0.5% and 10% by weight relative to the total weight of the composition.

Semi-Crystalline Polymer

The composition according to the invention may also advantageously comprise at least one semi-crystalline polymer of organic structure whose melting point is greater than or equal to 30° C.

Preferably, the total amount of semi-crystalline polymer(s) represents from 0.1% to 45% of the total weight of the composition, better still from 0.5% to 40%, for example from 1% to 35% by weight, better still from 1% to 20%, or from 3% to 30%, 5% to 30% or even 15% to 30%. It preferably represents from 2% to 10% by weight of the composition.

For the purposes of the invention, the term “polymers” means compounds containing at least two repeating units, preferably at least three repeating units and more especially at least ten repeating units.

For the purposes of the invention, the term “semi-crystalline polymer” means polymers comprising a crystallizable portion and an amorphous portion in the backbone and having a first-order reversible change of phase temperature, in particular of melting (solid-liquid transition). The crystallizable portion is either a side chain (or pendent chain) or a block in the backbone.

When the crystallizable portion of the semi-crystalline polymer is a block of the polymer backbone, this crystallizable block has a different chemical nature from that of the amorphous blocks; in this case, the semi-crystalline polymer is a block copolymer, for example of the diblock, triblock or multiblock type.

When the crystallizable portion is a chain that is pendent on the backbone, the semi-crystalline polymer may be a homopolymer or a copolymer.

The terms “organic compound” and “having an organic structure” mean compounds containing carbon atoms and hydrogen atoms and optionally heteroatoms such as S, O, N or P, alone or in combination.

The melting point of the semi-crystalline polymer is preferably less than 150° C.

The melting point of the semi-crystalline polymer is preferably greater than or equal to 30° C. and less than 100° C. More preferably, the melting point of the semi-crystalline polymer is preferably greater than or equal to 30° C. and less than 70° C.

The semi-crystalline polymer(s) according to the invention are solid at room temperature (25° C.) and atmospheric pressure (760 mmHg), with a melting point of greater than or equal to 30° C. The melting point values correspond to the melting point measured using a differential scanning calorimeter (DSC), such as the calorimeter sold under the name DSC 30 by the company Mettler, with a temperature rise of 5 or 10° C. per minute (the melting point under consideration is the point corresponding to the temperature of the most endothermic peak of the thermogram).

The semi-crystalline polymer(s) according to the invention preferably have a melting point that is higher than the temperature of the keratinous support intended to receive the composition, in particular the skin or the lips.

According to the invention, the semi-crystalline polymers are advantageously soluble in the fatty phase, especially to at least 1% by weight, at a temperature that is higher than their melting point. Besides the crystallizable chains or blocks, the blocks of the polymers are amorphous.

For the purposes of the invention, the expression “crystallizable chain or block” means a chain or block which, if it were obtained alone, would change from the amorphous state to the crystalline state reversibly, depending on whether one is above or below the melting point. For the purposes of the invention, a “chain” is a group of atoms, which are pendent or lateral relative to the polymer backbone. A “block” is a group of atoms belonging to the backbone, this group constituting one of the repeating units of the polymer.

Preferably, the polymer backbone of the semi-crystalline polymers is soluble in the fatty phase at a temperature above their melting point.

Preferably, the crystallizable blocks or chains of the semi-crystalline polymers represent at least 30% of the total weight of each polymer and better still at least 40%. The semi-crystalline polymers containing crystallizable side chains are homopolymers or copolymers. The semi-crystalline polymers of the invention containing crystallizable blocks are block or multiblock copolymers. They may be obtained by polymerizing a monomer containing reactive (or ethylenic) double bonds or by polycondensation. When the polymers of the invention are polymers containing crystallizable side chains, these side chains are advantageously in random or statistical form.

Preferably, the semi-crystalline polymers of the invention are of synthetic origin.

According to one preferred embodiment, the semi-crystalline polymer is chosen from:

-   -   homopolymers and copolymers comprising units resulting from the         polymerization of one or more monomers bearing crystallizable         hydrophobic side chains,     -   polymers bearing in the backbone at least one crystallizable         block,     -   polycondensates of aliphatic or aromatic or aliphatic/aromatic         polyester type,     -   copolymers of ethylene and propylene prepared via metallocene         catalysis.

The semi-crystalline polymers that may be used in the invention may be chosen in particular from:

-   -   block copolymers of polyolefins of controlled crystallization,         whose monomers are described in EP-A-0 951 897,     -   polycondensates, especially of aliphatic or aromatic polyester         type or of aliphatic/aromatic polyester type,     -   copolymers of ethylene and propylene prepared via metallocene         catalysis,     -   homopolymers or copolymers bearing at least one crystallizable         side chain and homopolymers or copolymers bearing at least one         crystallizable block in the backbone, for instance those         described in document U.S. Pat. No. 5,156,911,     -   homopolymers or copolymers bearing at least one crystallizable         side chain, in particular bearing fluoro group(s), such as those         described in document WO-A-01/19333,     -   and mixtures thereof.

In the last two cases, the crystallizable side chain(s) or block(s) is (are) hydrophobic.

A) Semi-Crystalline Polymers Containing Crystallizable Side Chains

Mention may be made in particular of those defined in documents U.S. Pat. No. 5,156,911 and WO-A-01/19333.

They are homopolymers or copolymers comprising from 50% to 100% by weight of units resulting from the polymerization of one or more monomers bearing a crystallizable hydrophobic side chain.

These homopolymers or copolymers are of any nature, provided that they meet the conditions mentioned hereinbelow with, in particular, the characteristic of being soluble or dispersible in the fatty phase, by heating above their melting point mp. They can result:

-   -   from the polymerization, especially the free-radical         polymerization, of one or more monomers containing reactive or         ethylenic double bond(s) with respect to a polymerization,         namely a vinyl, (meth)acrylic or allylic group,     -   from the polycondensation of one or more monomers bearing         co-reactive groups (carboxylic acid, sulfonic acid, alcohol,         amine or isocyanate), for instance polyesters, polyurethanes,         polyethers or polyureas.

a) In general, the crystallizable units (chains or blocks) of the semi-crystalline polymers according to the invention are derived from monomer(s) containing crystallizable block(s) or chain(s), used for manufacturing semi-crystalline polymers. These polymers are chosen especially from homopolymers and copolymers resulting from the polymerization of at least one monomer containing crystallizable chain(s) that may be represented by formula X:

with M representing an atom of the polymer backbone,

C representing a crystallizable group, and

S representing a spacer.

The crystallizable chains “—S—C” may be aliphatic or aromatic, and optionally fluorinated or perfluorinated. “C” especially represents a group (CH₂)_(n), which may be linear or branched or cyclic, with n being an integer ranging from 12 to 40. Preferably, “C” is a linear group. Preferably, “S” and “C” are different.

When the crystallizable chains are hydrocarbon-based aliphatic chains, they comprise hydrocarbon-based alkyl chains containing at least 12 carbon atoms and not more than 40 carbon atoms and better still not more than 24 carbon atoms. They are especially aliphatic chains or alkyl chains containing at least 12 carbon atoms, and they are preferably C₁₄-C₂₄, preferably C₁₅-C₂₂ alkyl chains. When they are fluoroalkyl or perfluoroalkyl chains, they contain at least 11 carbon atoms, at least 6 of which carbon atoms are fluorinated.

As examples of semi-crystalline homopolymers or copolymers containing crystallizable chain(s), mention may be made of those resulting from the polymerization of one or more of the following monomers: (meth)acrylates of saturated alkyls with the alkyl group being C₁₄-C₂₄, perfluoroalkyl (meth)acrylates with a C₁₁-C₁₅ perfluoroalkyl group, N-alkyl(meth)acrylamides with the alkyl group being C₁₄ to C₂₄ with or without a fluorine atom, vinyl esters containing alkyl or perfluoroalkyl chains with the alkyl group being C₁₄ to C₂₄ (with at least 6 fluorine atoms per perfluoroalkyl chain), vinyl ethers containing alkyl or perfluoroalkyl chains with the alkyl group being C₁₄ to C₂₄ and at least 6 fluorine atoms per perfluoroalkyl chain, C₁₄ to C₂₄ α-olefins such as, for example, octadecene, para-alkylstyrenes with an alkyl group containing from 12 to 24 carbon atoms, and mixtures thereof.

When the polymers result from a polycondensation, the hydrocarbon-based and/or fluorinated crystallizable chains as defined above are borne by a monomer that may be a diacid, a diol, a diamine or a diisocyanate.

When the polymers that are the subject of the invention are copolymers, they additionally contain from 0 to 50% of groups Y which is a polar or non-polar monomer or a mixture of the two.

When Y is a polar monomer, it is either a monomer bearing polyoxyalkylenated groups (especially oxyethylenated and/or oxypropylenated groups), a hydroxyalkyl (meth)acrylate, for instance hydroxyethyl acrylate, (meth)acrylamide, an N-alkyl(meth)acrylamide, an N,N-dialkyl(meth)acrylamide such as, for example, N,N-diisopropylacrylamide or N-vinylpyrrolidone (NVP), N-vinylcaprolactam, a monomer bearing at least one carboxylic acid group, for instance (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid, or bearing a carboxylic acid anhydride group, for instance maleic anhydride, and mixtures thereof.

When Y is a non-polar monomer, it may be an ester of the linear, branched or cyclic alkyl (meth)acrylate type, a vinyl ester, an alkyl vinyl ether, an α-olefin, styrene or styrene substituted with a C₁ to C₁₀ alkyl group, for instance α-methylstyrene, or a macromonomer of the polyorganosiloxane type containing vinyl unsaturation.

For the purposes of the invention, the term “alkyl” means a saturated group especially of C₈ to C₂₄, except where otherwise mentioned.

Preferably, the semi-crystalline polymers containing a crystallizable side chain are alkyl (meth)acrylate or alkyl(meth)acrylamide homopolymers with an alkyl group as defined above, and especially of C₁₄-C₂₄, copolymers of these monomers with a hydrophilic monomer preferably of different nature from (meth)acrylic acid, for instance N-vinylpyrrolidone or hydroxyethyl (meth)acrylate, and mixtures thereof.

Advantageously, the semi-crystalline polymer(s) containing a crystallizable side chain has (have) a weight-average molecular mass Mp ranging from 5000 to 1 000 000, preferably from 10 000 to 800 000, preferentially from 15 000 to 500 000 and more preferably from 100 000 to 200 000.

As a particular example of a semi-crystalline polymer that may be used in the composition according to the invention, mention may be made of the Intelimer® products from the company Landec described in the brochure “Intelimer® polymers”, Landec IP22 (Rev. 4-97). These polymers are in solid form at room temperature (25° C.). They bear crystallizable side chains and have the preceding formula X. They are poly(C₁₀-C₃₀)alkyl acrylates, which are particularly suitable as semi-crystalline polymers that may be included in a composition in accordance with the present invention. These polymers may especially have a molecular weight ranging from 15 000 to 500 000 and preferably from 100 000 to 200 000.

For example, the product Intelimer® IPA 13-1 from the company Landec is chosen, which is a polystearyl acrylate with a molecular weight of about 145 000 and a melting point of 49° C.

The semi-crystalline polymers may especially be those described in Examples 3, 4, 5, 7 and 9 of U.S. Pat. No. 5,156,911, and more particularly from the copolymerization:

-   -   of acrylic acid, of hexadecyl acrylate and of isodecyl acrylate         in a 1/16/3 ratio,     -   of acrylic acid and of pentadecyl acrylate in a 1/19 ratio,     -   of acrylic acid, of hexadecyl acrylate and of ethyl acrylate in         a 2.5/76.5/20 ratio,     -   of acrylic acid, of hexadecyl acrylate and of methyl acrylate in         a 5/85/10 ratio,     -   of acrylic acid and of polyoctadecyl (meth)acrylate in a         2.5/97.5 ratio.

It is also possible to use the polymer Structure “O” from National Starch, such as the product described in document U.S. Pat. No. 5,736,125 with a melting point of 44° C.

The semi-crystalline polymers may in particular be semi-crystalline polymers with crystallizable pendent chains comprising fluoro groups, as described in Examples 1, 4, 6, 7 and 8 of document WO-A-01/19333.

It is also possible to use the semi-crystalline polymers obtained by copolymerization of stearyl acrylate and of acrylic acid or of NVP, as described in document U.S. Pat. No. 5,519,063 or EP-A-550 745.

It is also possible to use the semi-crystalline polymers obtained by copolymerization of behenyl acrylate and of acrylic acid or of NVP, as described in documents U.S. Pat. No. 5,519,063 and EP-A-0 550 745 and more especially those described in Examples 3 and 4 below, of polymer preparation.

B) Polymers bearing at least one crystallizable block in the backbone

This is also a case of polymers that are soluble or dispersible in the fatty phase by heating above their melting point mp. These polymers are especially block copolymers consisting of at least two blocks of different chemical nature, one of which is crystallizable.

The polymer bearing at least one crystallizable block in the backbone may be chosen from block copolymers of olefin or of cycloolefin containing a crystallizable chain, for instance those derived from the block polymerization of:

-   -   cyclobutene, cyclohexene, cyclooctene, norbornene (i.e.         bicyclo(2,2,1)-2-heptene), 5-methylnorbornene,         5-ethylnorbornene, 5,6-dimethylnorbornene,         5,5,6-trimethylnorbornene, 5-ethylidenenorbornene,         5-phenylnorbornene, 5-benzylnorbornene, 5-vinylnorbornene,         1,4,5,8-dimethano-1,2,3,4,4a,5,8a-octahydronaphthalene,         dicyclopentadiene, or mixtures thereof, with     -   ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene,         4-methyl-1-pentene, 1-octene, 1-decene or 1-eicosene, or         mixtures thereof,

and in particular copoly(ethylene/norbornene) blocks and (ethylene/propylene/ethylidene-norbornene) block terpolymers. Those resulting from the block copolymerization of at least two C₂-C₁₆, better still C₂-C₁₂ α-olefins such as those mentioned above and in particular block bipolymers of ethylene and of 1-octene may also be used.

The polymer bearing at least one crystallizable block in the backbone may be chosen from copolymers containing at least one crystallizable block, the rest of the copolymer being amorphous (at room temperature). These copolymers may also contain two crystallizable blocks of different chemical nature.

The preferred copolymers are those that simultaneously contain at room temperature a crystallizable block and an amorphous block that are both hydrophobic and lipophilic, sequentially distributed; mention may be made, for example, of polymers containing one of the crystallizable blocks and one of the amorphous blocks below:

-   -   Block that is crystallizable by nature, of polyester type, for         instance poly(alkylene terephthalate), or of polyolefin type,         for instance polyethylenes or polypropylenes.     -   Amorphous and lipophilic block, for instance: amorphous         polyolefins or copoly(olefin)s such as poly(isobutylene),         hydrogenated polybutadiene or hydrogenated poly(isoprene).

As examples of such copolymers containing a crystallizable block and an amorphous block, mention may be made of:

α) poly(ε-caprolactone)-b-poly(butadiene) block copolymers, preferably used hydrogenated, such as those described in the article D6 “Melting behavior of poly(-caprolactone)-block-polybutadiene copolymers” from S, Nojima, Macromolecules, 32, 3727-3734 (1999),

β) the hydrogenated block or multiblock poly(butylene terephthalate)-b-poly(isoprene) block copolymers cited in the article D7 “Study of morphological and mechanical properties of PP/PBT” by B. Boutevin et al., Polymer Bulletin, 34, 117-123 (1995),

γ) the poly(ethylene)-b-copoly(ethylene/propylene) block copolymers cited in the articles D8 “Morphology of semi-crystalline block copolymers of ethylene(ethylene-alt-propylene)” by P. Rangarajan et al., Macromolecules, 26, 4640-4645 (1993) and D9 “Polymer aggregates with crystalline cores: the system poly(ethylene)-poly(ethylene-propylene)” by P. Richter et al., Macromolecules, 30, 1053-1068 (1997),

δ) the poly(ethylene)-b-poly(ethylethylene) block copolymers cited in the general article D10 “Crystallization in block copolymers” by I. W. Hamley, Advances in Polymer Science, Vol. 148, 113-137 (1999).

C) Polycondensates of Aliphatic or Aromatic or Aliphatic/Aromatic Polyester Type

The polyester polycondensates may be chosen from aliphatic polyesters. Their molar mass is preferably greater than or equal to 200 and less than or equal to 10 000, and more preferably greater than or equal to 300 and less than or equal to 5000, preferably greater than or equal to 500 and greater than or equal to 2000 g/mol.

The polyester polycondensates are in particular chosen from polycaprolactones. In particular, the polycaprolactones may be chosen from ε-caprolactone homopolymers. The homopolymerization may be initiated with a diol, especially a diol containing from 2 to 10 atoms, such as diethylene glycol, 1,4-butanediol or neopentyl glycol.

Polycaprolactones may be used for example, especially those sold under the name CAPA® 240 (melting point of 68° C. and molecular weight of 4000), 223 (melting point of 48° C. and molecular weight of 2000), 222 (melting point of 48° C. and molecular weight of 2000), 217 (melting point of 44° C. and molecular weight of 1250), 2125 (melting point of 45° C. and molecular weight of 1250), 212 (melting point of 45° C. and molecular weight of 1000), 210 (melting point of 38° C. and molecular weight of 1000), 205 (melting point of 39° C. and molecular weight of 830) by the company Solvay, or PCL-300 and PCL-700 by the company Union Carbide.

CAPA® 2125 whose melting point is between 35 and 45° C. and whose molecular weight is equal to 1250 may be used in particular.

The semi-crystalline polymers in the composition of the invention may or may not be partially crosslinked, provided that the degree of crosslinking does not interfere with their dissolution or dispersion in the fatty phase by heating above their melting point. It may then be a chemical crosslinking, by reaction with a multifunctional monomer during the polymerization. It may also be a physical crosslinking which may, in this case, be due either to the establishment of bonds of hydrogen or dipolar type between groups borne by the polymer, such as, for example, the dipolar interactions between carboxylate ionomers, these interactions being of small amount and borne by the polymer backbone; or to a phase separation between the crystallizable blocks and the amorphous blocks borne by the polymer.

Preferably, the semi-crystalline polymers in the composition according to the invention are non-crosslinked.

D) Copolymers of Ethylene and Propylene Prepared Via Metallocene Catalysis

The semi-crystalline polymer of the composition of the invention may also be a polymer obtained via metallocene catalysis, such as those described in patent US 2007/0 031 361, the content of which is incorporated herein by reference.

These polymers are copolymers of ethylene and propylene prepared via metallocene catalysis, i.e. by polymerization at low pressure and in the presence of a metallocene catalyst.

The weight-average molecular mass (Mw) of these polymers obtained via metallocene catalysis described in this document is less than or equal to 25 000 g/mol and ranges, for example, from 2000 to 22 000 g/mol and better still from 4000 to 20 000 g/mol.

The number-average molecular mass (Mn) of these copolymers obtained via metallocene catalysis described in this document is preferably less than or equal to 15 000 g/mol and ranges, for example, from 1000 to 12 000 g/mol and better still from 2000 to 10 000 g/mol.

The polydispersity index I of the polymer is equal to the ratio of the weight-average molecular mass Mw to the number-average molecular mass Mn.

Preferably, the polydispersity index of the copolymers is between 1.5 and 10, preferably between 1.5 and 5, preferably between 1.5 and 3 and better still between 2 and 2.5.

The copolymers may be obtained in a known manner from ethylene and/or propylene monomers, for example via metallocene catalysis according to the process described in document EP 571 882, the content of which is incorporated herein by reference.

The copolymers of ethylene and propylene prepared via metallocene catalysis may be unmodified or “polar”-modified (i.e. modified such that they contain polar groups). The polar-modified copolymers may be prepared in a known manner from unmodified homopolymers and copolymers such as those described previously by oxidation with gases containing oxygen, such as air, or by grafting with polar monomers such as maleic acid or acrylic acid or alternatively derivatives of these acids. These two routes enabling polar modification of the polyolefins obtained via metallocene catalysis are described, respectively, in documents EP 890 583 and U.S. Pat. No. 5,998,547, for example, the content of these two documents being incorporated herein by reference.

According to the present invention, the polar-modified copolymers of ethylene and/or propylene prepared via metallocene catalysis that are particularly preferred are polymers modified such that they have hydrophilic properties. Examples that may be mentioned include ethylene and/or propylene homopolymers or copolymers modified by the presence of hydrophilic groups such as maleic anhydride, acrylate, methacrylate, polyvinylpyrrolidone (PVP), etc.

Ethylene and/or propylene homopolymers or copolymers modified by the presence of hydrophilic groups such as maleic anhydride or acrylate are particularly preferred.

Examples that may be mentioned include:

-   -   polypropylene polymers modified with maleic anhydride (PPMA)         sold by the company Clariant, or polypropylene-ethylene-maleic         anhydride copolymers, such as those sold by the company Clariant         under the name LicoCare, for instance LicoCare PP207 LP3349,         LicoCare CM401 LP3345, LicoCare CA301 LP3346 and LicoCare CA302         LP3347.

In the context of a composition for the lips, a polar-modified polymer with a low degree of crystallinity, preferably of less than 40%, will be preferred.

The compositions may also comprise at least one film-forming polymer.

Additional Polymer

The compositions according to the invention may contain a film-forming polymer.

In the present invention, the term “film-forming polymer” means a polymer that is capable, by itself or in the presence of an auxiliary film-forming agent, of forming a macroscopically continuous deposit on keratin materials. The composition may comprise an aqueous phase, and the film-forming polymer may be present in this aqueous phase. In this case, it will preferably be a polymer in dispersion or an amphiphilic or associative polymer.

The term “polymer in dispersion” means water-insoluble polymers present in the form of particles of variable size. The polymer may or may not be crosslinked. The size of the polymer particles is typically between 25 and 500 nanometres and preferably between 50 and 200 nanometres. The following polymers in aqueous dispersion may be used: Ultrasol 2075 from Ganz Chemical, Daitosol 5000 AD from Daito Kasei, Avalure UR 450 from Noveon, DynamX from National Starch, Syntran 5760 from Interpolymer, Acusol OP 301 from Röhm & Haas, and Neocryl A 1090 from Avecia.

The acrylic dispersions sold under the names Neocryl XK-90®, Neocryl A-1070®, Neocryl A-1090®, Neocryl BT-62®, Neocryl A-1079® and Neocryl A-523® by the company Avecia-Neoresins, Dow Latex 432® by the company Dow Chemical, Daitosol 5000 AD® or Daitosol 5000 SJ® by the company Daito Kasey Kogyo; Syntran 5760® by the company Interpolymer, Soltex OPT by the company Röhm & Haas, aqueous dispersions of acrylic or styrene/acrylic polymers sold under the brand name Joncryl® by the company Johnson Polymer, or the aqueous dispersions of polyurethane sold under the names Neorez R-981® and Neorez R-974® by the company Avecia-Neoresins, Avalure UR-405®, Avalure UR-410®, Avalure UR-425®, Avalure UR-450®, Sancure 875®, Sancure 861®, Sancure 878® and Sancure 2060® by the company Goodrich, Impranil 85® by the company Bayer and Aquamere H-1511® by the company Hydromer; the sulfopolyesters sold under the brand name Eastman AQ® by the company Eastman Chemical Products, and vinyl dispersions, for instance Mexomer PAM® from the company Chimex, and mixtures thereof, are other examples of aqueous dispersions of water-dispersible film-forming polymer particles.

The term “amphiphilic or associative polymers” means polymers comprising one or more hydrophilic parts that make them partially water-soluble and one or more hydrophobic parts via which the polymers associate or interact. The following associative polymers may be used: Nuvis FX 1100 from Elementis, Aculyn 22, Aculyn 44 and Aculyn 46 from Röhm & Haas, Viscophobe DB 1000 from Amerchol. Diblock copolymers formed from a hydrophilic block (polyacrylate or polyethylene glycol) and from a hydrophobic block (polystyrene or polysiloxane) may also be used.

The composition may comprise an oily phase and the film-forming polymer may be present in this oily phase. The polymer may then be in dispersion or in solution.

As examples of lipodispersible non-aqueous film-forming polymer dispersions in the form of non-aqueous dispersions of polymer particles in one or more silicone and/or hydrocarbon-based oils, which may be surface-stabilized with at least one stabilizer, especially a block, grafted or random polymer, mention may be made of acrylic dispersions in isododecane, for instance Mexomer PAP® from the company Chimex, and dispersions of particles of a grafted ethylenic polymer, preferably an acrylic polymer, in a liquid fatty phase, the ethylenic polymer advantageously being dispersed in the absence of additional stabilizer at the surface of the particles as described especially in document WO 04/055 081.

Among the film-forming polymers that may be used in the composition of the present invention, mention may be made of synthetic polymers, of free-radical type or of polycondensate type, and polymers of natural origin, and mixtures thereof.

The expression “free-radical film-forming polymer” means a polymer obtained by polymerization of unsaturated and especially ethylenically unsaturated monomers, each monomer being capable of homopolymerizing (unlike polycondensates).

The film-forming polymers of free-radical type may especially be vinyl polymers or copolymers, especially acrylic polymers.

The vinyl film-forming polymers may result from the polymerization of ethylenically unsaturated monomers containing at least one acidic group and/or esters of these acidic monomers and/or amides of these acidic monomers.

Monomers bearing an acidic group that may be used are α,β-ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or itaconic acid. (Meth)acrylic acid and crotonic acid are preferably used, and more preferably (meth)acrylic acid.

The esters of acidic monomers are advantageously chosen from (meth)acrylic acid esters (also known as (meth)acrylates), especially (meth)acrylates of an alkyl, in particular of a C₁-C₃₀ and preferably C₁-C₂₀ alkyl, (meth)acrylates of an aryl, in particular of a C₆-C₁₀ aryl, and (meth)acrylates of a hydroxyalkyl, in particular of a C₂-C₆ hydroxyalkyl.

The film-forming polymer may be chosen from block or random polymers and/or copolymers especially comprising polyurethanes, polyacrylics, silicones, fluoro polymers, butyl rubbers, ethylene copolymers, natural gums and polyvinyl alcohols, and mixtures thereof.

The vinyl film-forming polymers may also result from the homopolymerization or copolymerization of monomers chosen from vinyl esters and styrene monomers.

Examples of vinyl esters that may be mentioned are vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butylbenzoate.

Styrene monomers that may be mentioned are styrene and α-methylstyrene.

Among the film-forming polycondensates that may be mentioned are polyurethanes, polyesters, polyesteramides, polyamides, epoxyester resins and polyureas.

The polyurethanes may be chosen from anionic, cationic, nonionic and amphoteric polyurethanes, polyurethane-acrylics, polyurethane-polyvinylpyrrolidones, polyester-polyurethanes, polyether-polyurethanes, polyureas and polyurea-polyurethanes, and mixtures thereof.

The polyesters may be obtained, in a known manner, by polycondensation of dicarboxylic acids with polyols, especially diols.

According to one example of a composition according to the invention, the film-forming polymer may be a polymer dissolved in a liquid fatty phase comprising organic solvents or oils (the film-forming polymer is thus said to be a liposoluble polymer). The liquid fatty phase preferably comprises a volatile oil, optionally mixed with a non-volatile oil.

Examples of liposoluble polymers that may be mentioned are copolymers of vinyl ester (the vinyl group being directly linked to the oxygen atom of the ester group and the vinyl ester containing a saturated, linear or branched hydrocarbon-based radical of 1 to 19 carbon atoms, linked to the carbonyl of the ester group) and of at least one other monomer which may be a vinyl ester (other than the vinyl ester already present), an α-olefin (containing from 8 to 28 carbon atoms), an alkyl vinyl ether (in which the alkyl group comprises from 2 to 18 carbon atoms) or an allylic or methallylic ester (containing a saturated, linear or branched hydrocarbon-based radical of 1 to 19 carbon atoms, linked to the carbonyl of the ester group).

These copolymers may be crosslinked with the aid of crosslinking agents, which may be either of the vinyl type or of the allylic or methallylic type, such as tetraallyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate and divinyl octadecanedioate.

Examples of liposoluble film-forming polymers that may be mentioned include copolymers of a vinyl ester and of at least one other monomer that may be a vinyl ester, especially vinyl neodecanoate, vinyl benzoate and vinyl t-butylbenzoate, an α-olefin, an alkyl vinyl ether or an allylic or methallylic ester.

Examples of liposoluble film-forming polymers that may also be mentioned are liposoluble copolymers, and in particular those resulting from the copolymerization of vinyl esters containing from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, and alkyl radicals containing from 10 to 20 carbon atoms.

Such liposoluble copolymers may be chosen from copolymers of polyvinyl stearate, polyvinyl stearate crosslinked with the aid of divinylbenzene, of diallyl ether or of diallyl phthalate, polystearyl (meth)acrylate, polyvinyl laurate and polylauryl (meth)acrylate, it being possible for these poly(meth)acrylates to be crosslinked with the aid of ethylene glycol dimethacrylate or tetraethylene glycol dimethacrylate.

The liposoluble copolymers defined above are known and are described in particular in patent application FR-A-2 232 303; they may have a weight-average molecular weight ranging from 2000 to 500 000 and preferably from 4000 to 200 000.

As liposoluble film-forming polymers that may be used in the invention, mention may also be made of polyalkylenes and in particular copolymers of C2-C20 alkenes, such as polybutene, alkylcelluloses with a linear or branched, saturated or unsaturated C1-C8 alkyl radical, for instance ethylcellulose and propylcellulose.

The composition according to the invention may comprise a plasticizer that promotes the formation of a film with the film-forming polymer. Such a plasticizer may be chosen from any compound known to those skilled in the art as being capable of fulfilling the desired function.

The compositions may also comprise at least one polymer comprising at least two groups capable of interacting via hydrogen bonding.

Polymer Comprising at Least Two Groups Capable of Interacting Via Hydrogen Bonds

According to one particular embodiment, the polymer comprising at least two groups capable of interacting via hydrogen bonding is present in the composition in a total content ranging from 0.5% to 50% by weight relative to the total weight of the composition, preferably ranging from 5% to 50% by weight and better still ranging from 8% to 45% by weight, for example ranging from 10% to 40% by weight, relative to the total weight of the composition.

According to the invention, the polymer comprising at least two groups capable of interacting via hydrogen bonding may belong to the following two families:

1) polymers comprising at least two groups capable of establishing hydrogen interactions, these two groups being located in the polymer chain, and/or

2) polymers comprising at least two groups capable of establishing hydrogen interactions, these two groups being located on grafts or branches.

For the purposes of the invention, the term “polymer” means a compound containing at least two repeating units and preferably at least three repeating units.

For the purposes of the invention, the term “repeating units” means a unit comprising from 2 to 80 carbon atoms and preferably from 2 to 60 carbon atoms, bearing hydrogen atoms and optionally oxygen atoms, which may be linear, branched or cyclic, and saturated or unsaturated. These units each also comprise one or more non-pendent heteroatoms that are in the polymer backbone. These heteroatoms are chosen from nitrogen, sulfur, phosphorus and silicon atoms and combinations thereof, optionally combined with one or more oxygen atoms.

Preferably, these groups are chosen from amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino and biguanidino groups, and combinations thereof.

As polymers comprising at least two groups capable of interacting via hydrogen bonding, examples that may be mentioned include:

-   -   polymers with a weight-average molecular mass of less than 100         000, comprising a) a polymer backbone with hydrocarbon-based         repeating units containing at least one heteroatom, and         optionally b) at least one pendent fatty chain and/or at least         one terminal fatty chain, optionally functionalized, containing         from 6 to 120 carbon atoms and being linked to these         hydrocarbon-based units, as described in patent applications         WO-A-02/056 847 and WO-A-02/47619, the content of which is         incorporated herein by reference; in particular polyamide resins         (especially comprising alkyl groups containing from 12 to 22         carbon atoms) such as those described in U.S. Pat. No.         5,783,657, the content of which is incorporated herein by         reference,     -   silicone polyamide resins as described in patent application         EP-A-1 266 647, and in the French patent application filed under         No. 0 216 039, the content of which is incorporated herein by         reference,     -   organopolysiloxanes comprising at least one carboxyl group, and         preferably organopolysiloxanes comprising at least two carboxyl         groups, per unit.

Such polymers comprising at least two groups capable of interacting via hydrogen bonding are described especially in patent application EP-A-1 400 234, the content of which is incorporated herein by reference, and are described in greater detail hereinbelow.

Silicone Polymer

According to a first embodiment of the invention, the polymer comprising at least two groups capable of interacting via hydrogen bonding is a silicone polyamide.

The silicone polyamides are preferably solid at room temperature (25° C.) and atmospheric pressure (760 mmHg).

The silicone polyamides of the composition of the invention may be polymers of the polyorganosiloxane type, for instance those described in documents U.S. Pat. No. 5,874,069, U.S. Pat. No. 5,919,441, U.S. Pat. No. 6,051,216 and U.S. Pat. No. 5,981,680.

According to the invention, the silicone polymers may belong to the following two families:

(1) polyorganosiloxanes comprising at least two amide groups, these two groups being located in the polymer chain, and/or

(2) polyorganosiloxanes comprising at least two amide groups, these two groups being located on grafts or branches.

A) According to a first variant, the silicone polymers are polyorganosiloxanes as defined above in which the amide units are located in the polymer chain.

The silicone polyamides may more particularly be polymers comprising at least one unit corresponding to the general formula I:

in which:

1) G′ represents C(O) when G represents —C(O)—NH—Y—NH—, and G′ represents —NH— when G represents —NH—C(O)—Y—C(O)—,

2) R⁴, R⁶, R⁶ and R⁷, which may be identical or different, represent a group chosen from:

-   -   linear, branched or cyclic, saturated or unsaturated, C₁-C₄₀         hydrocarbon-based groups, possibly containing in their chain one         or more oxygen, sulfur and/or nitrogen atoms, and possibly being         partially or totally substituted with fluorine atoms,     -   C₆-C₁₀ aryl groups, optionally substituted with one or more         C₁-C₄ alkyl groups,     -   polyorganosiloxane chains possibly containing one or more         oxygen, sulfur and/or nitrogen atoms;

3) the groups X, which may be identical or different, represent a linear or branched C₁-C₃₀ alkylenediyl group, possibly containing in its chain one or more oxygen and/or nitrogen atoms;

4) Y is a saturated or unsaturated, C₁-C₅₀ linear or branched divalent alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene group, possibly comprising one or more oxygen, sulfur and/or nitrogen atoms, and/or bearing as substituent one of the following atoms or groups of atoms: fluorine, hydroxyl, C₃-C₈ cycloalkyl, C₁-C₄₀ alkyl, C₅-C₁₀ aryl, phenyl optionally substituted with 1 to 3 C₁-C₃ alkyl, C₁-C₃ hydroxyalkyl and C₁-C₆ aminoalkyl groups; or

5) Y represents a group corresponding to the formula:

in which

-   -   T represents a linear or branched, saturated or unsaturated,         C₃-C₂₄ trivalent or tetravalent hydrocarbon-based group         optionally substituted with a polyorganosiloxane chain, and         possibly containing one or more atoms chosen from O, N and S, or         T represents a trivalent atom chosen from N, P and Al, and     -   R⁸ represents a linear or branched C₁-C₅₀ alkyl group or a         polyorganosiloxane chain, possibly comprising one or more ester,         amide, urethane, thiocarbamate, urea, thiourea and/or         sulfonamide groups, which may possibly be linked to another         chain of the polymer;

6) n is an integer ranging from 2 to 500 and preferably from 2 to 200, and m is an integer ranging from 1 to 1000, preferably from 1 to 700 and better still from 6 to 200.

According to one embodiment of the invention, 80% of the groups R⁴, R⁵, R⁶ and R⁷ of the polymer are preferably chosen from methyl, ethyl, phenyl and 3,3,3-trifluoropropyl groups. According to another embodiment, 80% of the groups R⁴, R⁵, R⁶ and R⁷ of the polymer are methyl groups.

Preferably, Y represents a group chosen from:

a) linear C₁ to C₂₀ and preferably C₁ to C₁₀ alkylene groups,

b) branched C₃₀ to C₅₆ alkylene groups possibly comprising rings and unconjugated unsaturations,

c) C₅-C₆ cycloalkylene groups,

d) phenylene groups optionally substituted with one or more C₁ to C₄₀ alkyl groups,

e) C₁ to C₂₀ alkylene groups comprising from 1 to 5 amide groups,

f) C₁ to C₂₀ alkylene groups comprising one or more substituents chosen from hydroxyl, C₃ to C₈ cycloalkane, C₁ to C₃ hydroxyalkyl and C₁ to C₆ alkylamine groups,

g) polyorganosiloxane chains of formula:

in which R⁴, R⁵, R⁶, R⁷ and m are as defined above.

B) According to the second variant, the silicone polyamides may be polymers comprising at least one unit corresponding to formula (II):

in which

-   -   R⁴ and R⁶, which may be identical or different, are as defined         above for formula (I),     -   R¹⁰ represents a group as defined above for R⁴ and R⁶, or         represents a group of formula —X-G″—R¹² in which X is as defined         above for formula (I) and R¹² represents a hydrogen atom or a         linear, branched or cyclic, saturated or unsaturated, C₁-C₅₀         hydrocarbon-based group optionally comprising in its chain one         or more atoms chosen from O, S and N, optionally substituted         with one or more fluorine atoms and/or one or more hydroxyl         groups, or a phenyl group optionally substituted with one or         more C₁-C₄ alkyl groups,

and G″ represents —C(O)NH— and —HN—C(O)—,

-   -   R¹¹ represents a group of formula —X-G″—R¹² in which X, G″ and         R¹² are as defined above,     -   m₁ is an integer ranging from 1 to 998, and     -   m₂ is an integer ranging from 2 to 500.

According to the invention, the silicone polymer may be a homopolymer, i.e. a polymer comprising several identical units, in particular units of formula (I) or of formula (II).

According to the invention, it is also possible to use a polymer consisting of a copolymer comprising several different units of formula (I), i.e. a polymer in which at least one of the groups R⁴, R⁵, R⁶, R⁷, X, G, Y, m and n is different in one of the units. The copolymer may also be formed from several units of formula (II), in which at least one of the groups R⁴, R⁶, R¹⁰, R¹¹, m₁ and m₂ is different in at least one of the units.

It is also possible to use a polymer comprising at least one unit of formula (I) and at least one unit of formula (II), the units of formula (I) and the units of formula (II) possibly being identical to or different from each other.

According to one variant of the invention, it is also possible to use a polymer furthermore comprising at least one hydrocarbon-based unit comprising two amide groups, chosen from ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino and biguanidino groups, and combinations thereof.

These copolymers may be block polymers or grafted polymers.

In formulae (I) and (II), the alkylene group representing X or Y can optionally contain in its alkylene part at least one of the following components:

1) one to five amide, urea, urethane or carbamate groups,

2) a C₅ or C₆ cycloalkyl group, and

3) a phenylene group optionally substituted with 1 to 3 identical or different C₁-C₃ alkyl groups.

In formulae (I) and (II), the alkylene groups may also be substituted with at least one component chosen from the group consisting of:

-   -   a hydroxyl group,     -   a C₃ to C₈ cycloalkyl group,     -   one to three C₁ to C₄₀ alkyl groups,     -   a phenyl group optionally substituted with one to three C₁ to C₃         alkyl groups,     -   a C₁ to C₃ hydroxyalkyl group, and     -   a C₁ to C₆ aminoalkyl group.

In these formulae (I) and (II), Y may also represent:

in which R⁸ represents a polyorganosiloxane chain and T represents a group of formula:

in which a, b and c are, independently, integers ranging from 1 to 10, and R¹³ is a hydrogen atom or a group such as those defined for R⁴, R⁵, R⁶ and R⁷.

In formulae (I) and (II), R⁴, R⁵, R⁶ and R⁷ preferably represent, independently, a linear or branched C₁ to C₄₀ alkyl group, preferably a CH₃, C₂H₅, n-C₃H₇ or isopropyl group, a polyorganosiloxane chain or a phenyl group optionally substituted with one to three methyl or ethyl groups.

As has been seen previously, the polymer may comprise identical or different units of formula (I) or (II).

Thus, the polymer may be a polyamide containing several units of formula (I) or (II) of different lengths, i.e. a polyamide corresponding to formula (III):

in which X, Y, n and R⁴ to R⁷ have the meanings given above, m₁ and m₂, which are different, are chosen in the range from 1 to 1000, and p is an integer ranging from 2 to 300.

In this formula, the units may be structured to form either a block copolymer, or a random copolymer or an alternating copolymer. In this copolymer, the units may be not only of different lengths, but also of different chemical structures, for example containing different groups Y. In this case, the polymer may correspond to formula IV:

in which R⁴ to R⁷, X, Y, m₁, m₂, n and p have the meanings given above and Y¹ is different from Y but chosen from the groups defined for Y. As previously, the various units may be structured to form either a block copolymer, or a random copolymer or an alternating copolymer.

In this first embodiment of the invention, the silicone polymer may also be formed from a grafted copolymer. Thus, the polyamide containing silicone units may be grafted and optionally crosslinked with silicone chains containing amide groups. Such polymers may be synthesized with trifunctional amines.

According to the invention, as has been seen previously, the siloxane units may be in the main chain or backbone of the polymer, but they may also be present in grafted or pendent chains. In the main chain, the siloxane units may be in the form of segments as described above. In the pendent or grafted chains, the siloxane units may appear individually or in segments.

According to one embodiment variant of the invention, a copolymer of silicone polyamide and of hydrocarbon-based polyamide, or a copolymer comprising units of formula (I) or (II) and hydrocarbon-based polyamide units, may be used. In this case, the polyamide-silicone units may be located at the ends of the hydrocarbon-based polyamide.

Advantageously, the composition comprises at least one polyamide/polydimethylsiloxane polymer, especially a polymer of general formula (I) with an index m of greater than 50, in particular greater than 75, especially between 50 and 200, for example of about 100.

Advantageously, the silicone polyamide of formula (I) has a weight-average molecular mass ranging from 10 000 to 500 000 g/mol.

More preferably, X and Y independently represent a group chosen from linear C₁ to C₂₀ and preferably C₁ to C₁₀ alkylene groups.

As examples of polymers that may be used, mention may be made of one of the silicone polyamides obtained in accordance with Examples 1 to 3 of document U.S. Pat. No. 5,981,680, such as the product sold under the reference DC 2-8179 by Dow Corning.

According to one embodiment variant of the invention, the polymer consists of a homopolymer or copolymer comprising urethane or urea groups. These polymers are described in detail in patent application WO 2003/106 614.

The first composition may contain, in place of the silicone polyamide, a polyorganosiloxane polymer containing two or more urethane and/or urea groups, either in the backbone of the polymer or on side chains or as pendent groups.

The polymers comprising at least two urethane and/or urea groups in the backbone may be polymers comprising at least one unit corresponding to the following formula:

in which R⁴, R⁵, R⁶, R⁷, X, Y, m and n have the meanings given above for formula (I), and U represents —O— or —NH—, such that:

corresponds to a urethane or urea group.

In this formula, Y may be a linear or branched C₁-C₄₀ alkylene group, optionally substituted with a C₁-C₁₅ alkyl group or a C₅-C₁₀ aryl group. Preferably, a —(CH₂)₆— group is used.

The polymer constituting the silicone polymer may be formed from silicone-urethane and/or silicone-urea units of different length and/or constitution, and may be in the form of block, sequenced or statistical (random) copolymers.

As in the case of the silicone polyamides of formula (I), (II) or (III), silicone polyurethanes or polyureas having units of different length and structure, in particular units of different lengths via the number of silicone units, may be used in the invention.

The polymers and copolymers used in the composition of the invention advantageously have a transition temperature from the solid state to the liquid state ranging from 45° C. to 190° C. Preferably, they have a transition temperature from the solid state to the liquid state ranging from 70 to 130° C. and better still from 80° C. to 105° C.

The silicone polyamide may be present in the first composition in a total content ranging from 0.5% to 70% by weight relative to the total weight of the composition, preferably ranging from 5% to 50% by weight, better still ranging from 8% to 45% by weight and preferably ranging from 10% to 40% by weight relative to the total weight of the composition.

Hydrocarbon-Based Polymer

According to a second embodiment of the invention, the polymer comprising at least two groups capable of interacting via hydrogen bonding is a polymer with a weight-average molecular mass of less than 100 000, comprising a) a polymer backbone with hydrocarbon-based repeating units containing at least one heteroatom, and optionally b) at least one pendent fatty chain and/or at least one terminal fatty chain, optionally functionalized, containing from 6 to 120 carbon atoms and being linked to these hydrocarbon-based units, as described in patent applications WO-A-02/056 847 and WO-A-02/47619, the content of which is incorporated herein by reference; in particular polyamide resins (especially comprising alkyl groups containing from 12 to 22 carbon atoms) such as those described in U.S. Pat. No. 5,783,657, the content of which is incorporated herein by reference.

The polymer according to the invention is an undeformable solid at room temperature (25° C.)

For the purposes of the invention, the term “functionalized chains” means an alkyl chain comprising one or more functional groups or reagents chosen especially from hydroxyl, ether, oxyalkylene or polyoxyalkylene, halogen, including fluoro or perfluoro groups, and ester groups. In addition, the hydrogen atoms of one or more fatty chains may be at least partially replaced with fluorine atoms.

Preferably, the hydrocarbon-based repeating units comprise at least one nitrogen atom, in particular a non-pendent nitrogen atom. These units also advantageously comprise a carbonyl group.

The units containing a heteroatom are, in particular, amide units forming a backbone of the polyamide type, carbamate and/or urea units forming a polyurethane, polyurea and/or polyurea-urethane backbone. These units are preferably amide units. The pendent chains are advantageously linked directly to at least one of the heteroatoms of the polymer backbone.

Between the hydrocarbon-based units, this polymer may comprise silicone units or oxyalkylene units.

In addition, this polymer of the composition of the invention advantageously comprises from 40% to 98% of fatty chains relative to the total number of units containing a heteroatom and of fatty chains, and better still from 50% to 95%. The nature and proportion of the units containing a heteroatom depends on the nature of the fatty phase and is, in particular, similar to the polar nature of the fatty phase. Thus, the more the units containing a heteroatom are polar and in high proportion in the first polymer, which corresponds to the presence of several heteroatoms, the greater the affinity of the first polymer for polar oils. On the other hand, the less polar or even apolar the units containing a heteroatom or the lower their proportion, the greater the affinity of the first polymer for apolar oils.

This polymer is advantageously a polyamide. Thus, a subject of the invention is also a composition containing, in a cosmetically acceptable medium, at least one polyamide polymer with a weight-average molecular mass of less than 100 000, comprising a) a polymer backbone containing amide repeating units, and b) optionally at least one pendent fatty chain and/or at least one terminal chain, which may be functionalized, containing from 8 to 120 carbon atoms and being linked to these amide units.

The pendent fatty chains are preferably linked to at least one of the nitrogen atoms of the amide units of this polymer.

In particular, the fatty chains of this polyamide represent from 40% to 98% of the total number of amide units and of fatty chains, and better still from 50% to 95%.

Advantageously, this polymer, and in particular this polyamide, of the composition according to the invention has a weight-average molecular mass of less than 100 000 (especially ranging from 1000 to 100 000), in particular less than 50 000 (especially ranging from 1000 to 50 000) and more particularly ranging from 1000 to 30 000, preferably from 2000 to 20 000 and better still from 2000 to 10 000.

This polymer, and in particular this polyamide, is insoluble in water, especially at 25° C. In particular, it contains no ionic groups.

As preferred polymers that may be used in the invention, mention may be made of polyamides branched with pendent fatty chains and/or terminal fatty chains containing from 6 to 120 carbon atoms and better still from 8 to 120 and in particular from 12 to 68 carbon atoms, each terminal fatty chain being linked to the polyamide backbone via at least one bonding group, in particular an ester. These polymers preferably comprise a fatty chain at each end of the polymer backbone and in particular of the polyamide backbone. Other bonding groups which may be mentioned are ether, amine, urea, urethane, thioester, thiourea and thiourethane groups.

These polymers are preferably polymers resulting from a polycondensation between a dicarboxylic acid containing at least 32 carbon atoms (in particular containing from 32 to 44 carbon atoms) and an amine chosen from diamines containing at least 2 carbon atoms (in particular from 2 to 36 carbon atoms) and triamines containing at least 2 carbon atoms (in particular from 2 to 36 carbon atoms). The diacid is preferably a dimer of a fatty acid containing ethylenic unsaturation containing at least 16 carbon atoms, preferably from 16 to 24 carbon atoms, for instance oleic acid, linoleic acid or linolenic acid. The diamine is preferably ethylenediamine, hexylenediamine or hexamethylenediamine. The triamine is, for example, ethylenetriamine. For the polymers comprising one or two terminal carboxylic acid groups, it is advantageous to esterify them with a monoalcohol containing at least four carbon atoms, preferably from 10 to 36 carbon atoms, better still from 12 to 24 and even better from 16 to 24, for example 18 carbon atoms.

These polymers are more especially those disclosed in document U.S. Pat. No. 5,783,657 from the company Union Camp. Each of these polymers in particular satisfies formula (I) below:

in which n denotes a number of amide units such that the number of ester groups represents from 10% to 50% of the total number of ester and amide groups; R₁ is, independently in each case, an alkyl or alkenyl group containing at least 4 carbon atoms and in particular from 4 to 24 carbon atoms; R₂ represents, independently in each case, a C₄ to C₄₂ hydrocarbon-based group, on condition that 50% of the groups R₂ represent a C₃₀ to C₄₂ hydrocarbon-based group; R₃ represents, independently in each case, an organic group containing at least 2 carbon atoms, hydrogen atoms and optionally one or more oxygen or nitrogen atoms; and R₄ represents, independently in each case, a hydrogen atom, a C₁ to C₁₀ alkyl group or a direct bond to R₃ or to another R₄, such that the nitrogen atom to which R₃ and R₄ are both attached forms part of a heterocyclic structure defined by R₄—N—R₃, with at least 50% of the groups R₄ representing a hydrogen atom.

In the particular case of formula (I), the terminal fatty chains that are optionally functionalized for the purposes of the invention are terminal chains linked to the last heteroatom, in this case nitrogen, of the polyamide backbone.

In particular, the ester groups of formula (I), which form part of the terminal and/or pendent fatty chains for the purposes of the invention, represent from 15% to 40% of the total number of ester and amide groups and better still from 20% to 35%. Furthermore, n is advantageously an integer ranging from 1 to 5 and better still greater than 2. Preferably, R₁ is a C₁₂ to C₂₂ and preferably C₁₆ to C₂₂ alkyl group. Advantageously, R₂ can be a C₁₀ to C₄₂ hydrocarbon-based (alkylene) group. Preferably, at least 50% and better still at least 75% of the groups R₂ are groups containing from 30 to 42 carbon atoms. The other groups R₂ are C₄ to C₁₉ and better still C₄ to C₁₂ hydrogen-containing groups. Preferably, R₃ represents a C₂ to C₃₆ hydrocarbon-based group or a polyoxyalkylene group and R₄ represents a hydrogen atom. Preferably, R₃ represents a C₂ to C₁₂ hydrocarbon-based group.

The hydrocarbon-based groups may be linear, cyclic or branched, and saturated or unsaturated groups. Moreover, the alkyl and alkylene groups may be linear or branched, and saturated or unsaturated groups.

In general, the polymers of formula (I) are in the form of mixtures of polymers, these mixtures also possibly containing a synthetic product corresponding to a compound of formula (I) in which n is 0, i.e. a diester.

As examples of polymers comprising at least two groups capable of interacting via hydrogen bonding, which may be used in the compositions according to the invention, mention may be made of the commercial products sold by the company Arizona Chemical under the names Uniclear 80 and Uniclear 100. They are sold, respectively, in the form of an 80% (in terms of active material) gel in a mineral oil and a 100% (in terms of active material) gel. They have a softening point of from 88 to 94° C. These commercial products are a mixture of copolymers of a C36 diacid condensed with ethylenediamine, having a weight-average molecular mass of about 6000. The terminal ester groups result from the esterification of the remaining acid endings with cetyl alcohol, stearyl alcohol or mixtures thereof (also known as cetylstearyl alcohol).

As polymers comprising at least two groups capable of interacting via hydrogen bonding, which may be used in the compositions according to the invention, mention may also be made of polyamide resins resulting from the condensation of an aliphatic dicarboxylic acid and a diamine (including compounds containing more than 2 carbonyl groups and 2 amine groups), the carbonyl and amine groups of adjacent individual units being condensed via an amide bond. These polyamide resins are, in particular, those sold under the brand name Versamid® by the companies General Mills Inc. and Henkel Corp. (Versamid 930, 744 or 1655) or by the company Olin Mathieson Chemical Corp. under the brand name Onamid®, in particular Onamid S or C. These resins have a weight-average molecular mass ranging from 6000 to 9000. For further information regarding these polyamides, reference may be made to the documents U.S. Pat. No. 3,645,705 and U.S. Pat. No. 3,148,125. More especially, Versamid® 930 or 744 is used.

The polyamides sold by the company Arizona Chemical under the references Uni-Rez (2658, 2931, 2970, 2621, 2613, 2624, 2665, 1554, 2623 and 2662) and the product sold under the reference Macromelt 6212 by the company Henkel may also be used. For further information regarding these polyamides, reference may be made to document U.S. Pat. No. 5,500,209.

It is also possible to use polyamide resins, such as those disclosed in U.S. Pat. No. 5,783,657 and U.S. Pat. No. 5,998,570.

The polymer present in the composition according to the invention advantageously has a softening point of greater than 65° C., which may be up to 190° C. It preferably has a softening point ranging from 70° C. to 130° C. and better still from 80° C. to 105° C.

Dyestuffs

The compositions according to the invention may advantageously contain a colouring agent, which may be chosen from water-soluble or liposoluble dyes, pigments and nacres, and mixtures thereof.

The composition according to the invention may also comprise one or more dyestuffs chosen from water-soluble dyes and pulverulent dyestuffs, for instance pigments, nacres and glitter flakes that are well known to those skilled in the art. The dyestuffs may be present in the composition in a content ranging from 0.01% to 50% by weight and preferably from 0.01% to 30% by weight, and in particular from 0.05% to 25% by weight, relative to the weight of the composition.

The term “pigments” should be understood as meaning white or coloured, mineral or organic particles, which are insoluble in an aqueous solution and which are intended to colour and/or opacify the resulting film.

The pigments may be present in a proportion of from 0.01% to 20% by weight, especially from 0.01% to 15% by weight and in particular from 0.02% to 10% by weight relative to the total weight of the cosmetic composition.

As mineral pigments that may be used in the invention, mention may be made of titanium oxide, zirconium oxide or cerium oxide, and also zinc oxide, iron oxide or chromium oxide, ferric blue, manganese violet, ultramarine blue and chromium hydrate.

They may also be pigments with a structure that may be, for example, of sericite/brown iron oxide/titanium dioxide/silica type. Such a pigment is sold, for example, under the reference Coverleaf NS or JS by the company Chemicals & Catalysts.

The dyestuff may also comprise a pigment with a structure that may be, for example, of silica microsphere type containing iron oxide. An example of a pigment having this structure is the product sold by the company Miyoshi under the reference PC Ball PC-LL-100 P, this pigment being formed from silica microspheres containing yellow iron oxide.

Among the organic pigments that may be used in the invention, mention may be made of carbon black, pigments of D&C type, lakes based on cochineal carmine or on barium, strontium, calcium or aluminium, or alternatively the diketopyrrolopyrroles (DPP) described in documents EP-A-542 669, EP-A-787 730, EP-A-787 731 and WO-A-96/08537.

The term “nacres” should be understood as meaning iridescent or non-iridescent coloured particles of any form, especially produced by certain molluscs in their shell, or else synthesized, and which have a colour effect by optical interference.

The nacres may be chosen from nacreous pigments such as titanium mica coated with an iron oxide, titanium mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with an organic dye and also nacreous pigments based on bismuth oxychloride. They may also be mica particles at the surface of which are superposed at least two successive layers of metal oxides and/or of organic dyestuffs.

Examples of nacres that may also be mentioned include natural mica coated with titanium oxide, with iron oxide, with natural pigment or with bismuth oxychloride.

Among the nacres available on the market, mention may be made of the mica-based nacres Timica, Flamenco and Duochrome sold by the company Engelhard, the Timiron nacres sold by the company Merck, the Prestige mica-based nacres, sold by the company Eckart, and the Sunshine synthetic mica-based nacres, sold by the company Sun Chemical.

The nacres may more particularly have a yellow, pink, red, bronze, orangey, brown, gold and/or coppery colour or tint.

As illustrations of nacres that may be used in the context of the present invention, mention may be made especially of the gold-coloured nacres sold especially by the company Engelhard under the name Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze nacres sold especially by the company Merck under the name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company Engelhard under the name Super bronze (Cloisonne); the orange nacres sold especially by the company Engelhard under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company Merck under the name Passion orange (Colorona) and Matte orange (17449) (Microna); the brown nacres sold especially by the company Engelhard under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); the nacres with a copper tint sold especially by the company Engelhard under the name Copper 340A (Timica); the nacres with a red tint sold especially by the company Merck under the name Sienna fine (17386) (Colorona); the nacres with a yellow tint sold especially by the company Engelhard under the name Yellow (4502) (Chromalite); the red nacres with a gold tint sold especially by the company Engelhard under the name Sunstone G012 (Gemtone); the pink nacres sold especially by the company Engelhard under the name Tan opale G005 (Gemtone); the black nacres with a gold tint sold especially by the company Engelhard under the name Nu antique bronze 240 AB (Timica), the blue nacres sold especially by the company Merck under the name Matte blue (17433) (Microna), the white nacres with a silvery tint sold especially by the company Merck under the name Xirona Silver, and the golden-green pink-orange nacres sold especially by the company Merck under the name Indian summer (Xirona), and mixtures thereof.

The term “dyes” should be understood as meaning compounds that are generally organic, which are soluble in fatty substances such as oils or in an aqueous-alcoholic phase.

The liposoluble dyes may be chosen from Sudan red, DC Red 17, DC Green 6, n-carotene, Sudan brown, DC Yellow 11, DC Violet 2, DC Orange 5 and quinoline yellow. The water-soluble dyes are, for example, beetroot juice or methylene blue.

The cosmetic composition according to the invention may also contain at least one material with a specific optical effect.

This effect is different from a simple conventional hue effect, i.e. a unified and stabilized effect as produced by standard dyestuffs, for instance monochromatic pigments. For the purposes of the invention, the term “stabilized” means lacking an effect of variability of the colour as a function of the angle of observation or alternatively in response to a temperature change.

For example, this material may be chosen from particles with a metallic tint, goniochromatic colouring agents, diffracting pigments, thermochromic agents, optical brighteners, and also fibres, especially interference fibres. Needless to say, these various materials may be combined so as to simultaneously afford two effects.

The particles with a metallic tint that may be used in the invention are chosen in particular from:

-   -   particles of at least one metal and/or of at least one metal         derivative,     -   particles comprising a monomaterial or multimaterial organic or         mineral substrate, at least partially coated with at least one         coat with a metallic tint comprising at least one metal and/or         at least one metal derivative, and     -   mixtures of the particles.

Among the metals that may be present in the particles, mention may be made, for example, of Ag, Au, Cu, Al, Ni, Sn, Mg, Cr, Mo, Ti, Zr, Pt, Va, Rb, W, Zn, Ge, Te and Se, and mixtures or alloys thereof. Ag, Au, Cu, Al, Zn, Ni, Mo and Cr and mixtures or alloys thereof (for example bronzes and brasses) are preferred metals.

The term “metal derivatives” is intended to denote compounds derived from metals, especially oxides, fluorides, chlorides and sulfides.

As illustrations of these particles, mention may be made of aluminium particles, such as those sold under the names Starbrite 1200 EAC® by the company Siberline, and Metalure® by the company Eckart.

Mention may also be made of copper metal powders or alloy mixtures such as the reference 2844 sold by the company Radium Bronze, metallic pigments such as aluminium or bronze, such as those sold under the name Rotosafe 700 from the company Eckart, the silica-coated aluminium particles sold under the name Visionaire Bright Silver from the company Eckart and metal alloy particles, for instance the silica-coated bronze (alloy of copper and zinc) powders sold under the name Visionaire Bright Natural Gold from the company Eckart.

They may also be particles comprising a glass substrate, such as those sold by the company Nippon Sheet Glass under the name Microglass Metashine.

The goniochromatic colouring agent may be chosen, for example, from multilayer interference structures and liquid-crystal colouring agents.

Examples of symmetrical multilayer interference structures that may be used in the compositions prepared in accordance with the invention are, for example, the following structures: Al/SiO₂/Al/SiO₂/Al, pigments having this structure being sold by the company DuPont de Nemours; Cr/MgF₂/Al/MgF₂/Cr, pigments having this structure being sold under the name Chromaflair by the company Flex; MoS₂/SiO₂/Al/SiO₂/MoS₂; Fe₂O₃/SiO₂/Al/SiO₂/Fe₂O₃, and Fe₂O₃/SiO₂/Fe₂O₃/SiO₂/Fe₂O₃, pigments having these structures being sold under the name Sicopearl by the company BASF; MoS₂/SiO₂/mica-oxide/SiO₂/MoS₂; Fe₂O₃/SiO₂/mica-oxide/SiO₂/Fe₂O₃; TiO₂/SiO₂/TiO₂ and TiO₂/Al₂O₃/TiO₂; SnO/TiO₂/SiO₂/TiO₂/SnO; Fe₂O₃/SiO₂/Fe₂O₃; SnO/mica/TiO₂/SiO₂/TiO₂/mica/SnO, pigments having these structures being sold under the name Xirona by the company Merck (Darmstadt). By way of example, these pigments may be the pigments of silica/titanium oxide/tin oxide structure sold under the name Xirona Magic by the company Merck, the pigments of silica/brown iron oxide structure sold under the name Xirona Indian Summer by the company Merck and the pigments of silica/titanium oxide/mica/tin oxide structure sold under the name Xirona Caribbean Blue by the company Merck. Mention may also be made of the Infinite Colors pigments from the company Shiseido. Depending on the thickness and the nature of the various layers, different effects are obtained. Thus, with the Fe₂O₃/SiO₂/Al/SiO₂/Fe₂O₃ structure, the colour changes from green-golden to red-grey for SiO₂ layers of 320 to 350 nm; from red to golden for SiO₂ layers of 380 to 400 nm; from violet to green for SiO₂ layers of 410 to 420 nm; from copper to red for SiO₂ layers of 430 to 440 nm.

Examples of pigments with a polymeric multilayer structure that may be mentioned include those sold by the company 3M under the name Color Glitter.

Examples of liquid-crystal goniochromatic particles that may be used include those sold by the company Chenix and also the products sold under the name Helicone® HC by the company Wacker.

Filler

A composition according to the invention may comprise a filler, especially in a total content ranging from 0.01% to 30%, in particular from 0.01% to 20% by weight, for example ranging from 0.1% to 15% or from 0.5% to 10% by weight relative to the total weight of the composition.

For the purposes of the present invention, the term “fillers” should be understood as meaning colourless or white, mineral or synthetic particles of any form, which are insoluble in the medium of the composition irrespective of the temperature at which the composition is manufactured. These fillers serve especially to modify the rheology or texture of the composition.

The fillers may be mineral or organic and of any shape, platelet-shaped, spherical or oblong, irrespective of the crystallographic form (for example lamellar, cubic, hexagonal, orthorhombic, etc.). Mention may be made of talc, mica, silica, kaolin, polyamide (Nylon®) powder (Orgasol® from Atochem), poly-β-alanine powder and polyethylene powder, powders of tetrafluoroethylene polymers (Teflon®), lauroyllysine, starch, boron nitride, hollow polymer microspheres such as those of polyvinylidene chloride/acrylonitrile, for instance Expancel® (Nobel Industrie) or of acrylic acid copolymers (Polytrap® from the company Dow Corning) and silicone resin microbeads (Tospearls® from Toshiba, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate, magnesium hydrogen carbonate, hydroxyapatite, hollow silica microspheres (Silica Beads® from Maprecos), glass or ceramic microcapsules, and metal soaps derived from organic carboxylic acids containing from 8 to 22 carbon atoms and preferably from 12 to 18 carbon atoms, for example zinc stearate, magnesium stearate or lithium stearate, zinc laurate or magnesium myristate.

They may also be particles comprising a copolymer, the copolymer comprising trimethylol hexyllactone. In particular, it may be a copolymer of hexamethylene diisocyanate/trimethylol hexyllactone. Such particles are especially commercially available, for example, under the name Plastic Powder D-400® or Plastic Powder D-800® from the company Toshiki.

Additional Usual Cosmetic Ingredients

The composition according to the invention may also comprise any usual cosmetic ingredient, which may be chosen especially from antioxidants, fragrances, preserving agents, neutralizers, surfactants, sunscreens, sweeteners, vitamins, moisturizers, emollients, hydrophilic or lipophilic active agents, free-radical scavengers and sequestrants, and mixtures thereof.

Needless to say, a person skilled in the art will take care to select the optional additional ingredients and/or the amount thereof such that the advantageous properties of the composition according to the invention are not, or are not substantially, adversely affected by the envisaged addition.

A person skilled in the art may select the appropriate galenical form, and also the method for preparing it, on the basis of his general knowledge, taking into account firstly the nature of the constituents used, especially their solubility in the support, and secondly the intended use of the composition.

Preferably, the composition according to the invention comprises less than 3% and better still less than 1% by weight of water relative to the total weight of the composition. Even more preferably, the composition is totally anhydrous. The term “anhydrous” especially means that water is preferably not deliberately added to the composition, but may be present in trace amount in the various compounds used in the composition.

The composition according to the invention may be intended for caring for and/or making up keratin materials, especially the lips and the skin, in particular the lips.

The examples that follow illustrate the invention in a non-limiting manner.

The amounts are expressed as weight percentages.

Application Devices

Examples will now be given of devices for, inter alia, performing a cosmetic treatment process comprising:

a) heating an application surface of a mass of solid product, using an artificial source of heat located to the exterior of the mass of product, especially an application surface of a wand of product, to bring it to a temperature above that of a portion of the mass of product remote from the application surface and which remains solid during the application, and

b) applying the application surface thus heated to an area to be treated, especially the skin or the lips.

The description of these devices is made with reference to the attached drawing, in which, as explained above:

FIG. 1 shows schematically, in elevation, an example of a conditioning and application device made in accordance with the invention,

FIG. 2 shows in isolation, with partial and schematic longitudinal cutaway, the cap of the device of FIG. 1,

FIG. 3 illustrates, schematically and partially, the heating of the wand by contact with a hot surface,

FIG. 4 represents, schematically and partially, one embodiment example of the heating member,

FIGS. 5 to 7 illustrate production details of variants of heating members,

FIG. 8 represents, schematically, an embodiment variant of the conditioning and application device,

FIG. 9 is a schematic and partial cutaway of the device of FIG. 8, after insertion in the corresponding housing of the case,

FIG. 10 shows a wand and associated support means,

FIG. 11 shows in elevation an embodiment variant of the conditioning and application device,

FIG. 12 is a partial and schematic longitudinal cutaway of the device of FIG. 11,

FIG. 13 is a partial and schematic longitudinal cutaway of an embodiment variant of the device,

FIG. 14 is a product conditioning variant, and

FIG. 15 described previously illustrates the measurement of the coefficient of dynamic friction.

The conditioning and application device 1 shown in FIG. 1 comprises a base part 2 that supports a mass of product according to the invention in the form of a wand S of product, and a cap 3 and that can be attached to the base part 2 to close the device 1 when not in use.

The base part 2 may be of any known type for removing the wand S gradually as it is consumed.

The base part 2 comprises, for example, two parts 5 and 6 that can rotate relative to each other, and a mechanism for transforming the relative rotation of the two parts 5 and 6 into an axial movement along the longitudinal axis X of the wand S.

The wand S is borne, for example, in this mechanism, by a cup 58 as shown in FIG. 10, comprising spurs 59 engaged in two pieces belonging, respectively, to parts 5 and 6, one of which comprises longitudinal rectilinear slits and the other spiral slits, such that a rotation of these two pieces is accompanied by an axial movement of the cup and of the wand S.

Examples of mechanisms that may be suitable for use are described in the publications U.S. Pat. No. 6,340,258, U.S. Pat. No. 6,086,276, U.S. Pat. No. 6,371,673, U.S. Pat. No. 5,171,096 and U.S. Pat. No. 7,293,926, the content of which is incorporated herein by reference.

The cap 3 comprises a heating device 10 for heating the end 11 of the wand S prior to its application to the keratin materials, for example the skin or the lips.

The heating device 10 may house a power source, not shown, for example containing one or more batteries or accumulators, and a heating member comprising, for example, an electrical resistance powered by the power source.

Examples of heating members that may be suitable for use are disclosed in US 2007/0 286 665 A1, for example.

The heating member is arranged so as to raise the temperature of a heating surface 13 which, in the example of FIGS. 1 and 2, may come into contact with the wand S, as shown in FIG. 3, so as to raise the temperature of the distal end 11 thereof.

The heating device 10 may comprise a switch 14 that allows the user to switch the heating device 10 on or off, and also an operating indicator 15, for example an indicator light that lights up when the heating surface 13 is undergoing heating.

The heating device 10 may optionally comprise any means for regulating the temperature of the heating surface 13, so that it does not exceed a predefined value.

When the heating surface is inaccessible to the user, a heating temperature that is higher but compatible with the product may be accepted. On the other hand, when the heating surface 13 may come into contact with the user, a temperature not exceeding 65° C. is preferred.

The heating device 10 may also, where appropriate, comprise a timer for heating the end 11 of the wand S only for a predefined time, so as to avoid premature wear of the electrical power source and/or to avoid bringing the wand assembly to an excessive temperature.

The heating device 10 may advantageously comprise any suitable sensor for preventing the start of functioning of the heating except in the case of effective contact of the heating surface with the end 11 of the wand S.

For example, the heating device 10 may comprise a contact pressure sensor between the heating surface 13 and the wand S, and permit heating of the heating surface 13 only in the case of veritable contact with the wand S.

The heating surface 13 may be defined, for example, by a contact piece 20, which is, for example, axially mobile along the axis X relative to the body 22 of the heating device 10 against the return action of an elastic return member 23, for instance a spring housed inside the contact piece 20, as illustrated in FIG. 4.

This FIG. 4 shows a heating device comprising an electrical resistance 25 placed in the bottom of the contact piece 20, so as to be as close as possible to the heating surface 13.

The contact piece 20 may comprise, for example, a metal that is a good heat conductor, with a low wall thickness, so as to have low thermal inertia. In certain embodiments, the contact piece 20 may, for example, comprise aluminium.

The heating surface 13 may be given any shape adapted to the geometry of the end 11 of the wand, for example a beveled shape substantially complementary to the shape of the end 11 of the wand S, as illustrated in FIGS. 1 and 2, or another shape, for example a concave shape towards the wand S, especially a spherical crown shape as illustrated in FIG. 5, a conical or frustoconical shape as illustrated in FIG. 6, or a substantially flat shape perpendicular to the axis X, as illustrated in FIG. 7.

When the shape of the heating surface 13 is not rotationally symmetric about the axis X, the device 1 may comprise rotational indexing means for the base part 2 and the cap 3 so as to enable attachment of the cap 3 to the base part 2 only in one predefined angular orientation between the two, in which the heating surface can come to rest in a predefined manner, which is compatible with its geometry, against the wand S.

The wand S, which is, for example, a lipstick wand, may have a cross section of between 0.1 and 5 cm², or even between 0.15 and 1 cm², and the device 1 may be used by first switching on the heating device 10 and then waiting for the time necessary for the end 11 of the wand that defines the application surface to be brought to the desired temperature.

Arrival at the operating temperature may be indicated, for example, by the indicator light 15, which may pass, for example, from being a continuous light indicating the startup of the device, to a flashing light or a colour change when the temperature is reached. Other methods for indicating the operating state may be used without, however, departing from the scope of the invention.

Once the end of the wand has been heated, the base part 2 may be separated from the cap 3 and the user can apply the product of the wand onto the lips or other keratin materials. Softening of the product at the end 11 of the wand ensures comfortable application and good transfer onto the lips, with a thick and optionally glossy deposit on application.

For example, the application is performed without using an applicator. In other words, only the composition, and more precisely the softened surface, comes into direct contact with the area to be treated.

The body of the wand S is at room temperature or at a slightly higher temperature, but insufficient to compromise the mechanical strength necessary to withstand the mechanical efforts generated by the application. The temperature difference between the application surface and the body of the wand, especially at the end opposite the application surface, is, for example, at least 20° C., or even at least 30° C. when the wand has its initial length, on the first use.

The device 1 may be used in a similar manner for making up the skin, and the wand may then be of greater cross section, where appropriate.

It may be that the heating device is not incorporated into a cap 3 of the conditioning device, but is present in a case 40 separate from the conditioning device of the wand S, as illustrated in FIGS. 8 and 9.

The case 40 may house a power source and/or may comprise a means for connecting to a power source, for example the mains supply, via a low-voltage transformer.

The case 40 may also comprise startup means 41, for instance an on/off switch, and also one or more indicator lights 42 and 55 to indicate the live power connection and/or the end of arrival at the operating temperature.

In the example of FIGS. 8 and 9, the case 40 comprises an aperture 46 into which the base part 2 may be at least partially introduced, as illustrated in FIG. 9, so as to bring the end 11 of the wand in the vicinity of a heating means 50 present in the case 40.

The aperture 46 has, for example, a cross section adapted to one of the pieces of the base part, so that the engagement of the base part in the case brings the end 11 of the wand into a predefined position, according to at least two spatial directions, relative to the heating means.

The case 40 may comprise any suitable sensor 51 for detecting the insertion of the base part 2 into the case 40 and optionally the positioning of the wand relative to the heating means.

Heating of the end of the wand S may take place by conduction, on contact with a hot surface, in the manner described above. In this case, the heating means comprises a heating surface that may be brought to the appropriate temperature by any heating means, for example an electrical resistance.

Heating of the end of the wand may also be performed without contact, for example by infrared radiation and/or convection, and/or by vibrations and/or wireless radiation, or any other source that produces heat.

As mentioned above, the case 40 may comprise any suitable sensor, especially an optical sensor, that is capable of evaluating the distance between the end 11 of the wand and the heating means 50, so as to switch on the heating means only when a predefined distance is respected and/or so as to control the heating power as a function of the remoteness between the heating means and the end of the wand S.

In certain variants, the heating means 50 may be a system of heating by emission of infrared radiation towards the end 11 of the wand, for example using a halogen or incandescent lamp, or by blowing hot air towards the end 11.

In certain variants, the end 11 of the wand S may also be heated by exposure to wireless radiation, for example microwaves, focused at the end 11 of the wand S.

In yet other variants, the end 11 of the wand S may be heated by ultrasonic vibrations.

In the embodiment variant of FIGS. 11 and 12, the heating device 60 comprises a heating means 62 that is an integral part of the base part 2 and that may comprise, as illustrated, a circular-shaped heating member 62, through which the wand S may pass. The heating member 62 has, for example, a cross section greater than or equal to that of the wand S.

The heating device 60 may comprise, for example, a control member 64 which the user may press to start the functioning of the heating member 62. The heating member 62 may comprise, for example, a heating resistance for heating the end 11 of the wand S by conduction, convection and/or radiation (for example infrared, microwave, etc. radiation).

Where appropriate, the heating member 62 may also participate in the application of the product associated with the wand S, and, to this end, may have a top face 70 of suitable shape, for example beveled.

To use the device in the example under consideration, the user can bring the end 11 of the wand to the heating member 62 and start the heating by pressing on the control member 64.

The heating device may comprise an indicator light 72 that indicates to the user that the heating member 62 is functioning.

The user can then stop the heating when he visually observes that the end 11 of the wand has become changed in appearance following the raising of the temperature, for example when it has become glossy.

The user can then optionally, at this moment, move the end 11 slightly higher upward so as to facilitate the application of the product, without contact with the heating member 62. As a variant, the user can apply the product via contact not only of the wand S, but also of the heating member 62, on the lips or the skin.

Where appropriate, the surface of the heating member 62 liable to come into contact with the skin may be flocked or may have a textured surface aspect that facilitates application.

In the variant shown in FIG. 13, the wand S passes through a heating member 62 defining an aperture whose cross section is narrower than the cross section of the body of the wand.

Softening of the wand S on contact with the heating member 62 may thus be accompanied, in this example, by a deformation of the wand through the heating member 62. This may increase the precision of application of the product and prevent the wand S from being advanced relative to the heating member 62 before sufficient softening has been reached.

The outer surface of the heating member 62 may be tapered, as shown in FIG. 13, so as to reduce the contact surface between the treated area and the heating member 62.

FIG. 14 shows an embodiment variant in which the mass of product S associated with the wand S is supported by a stem 200, and is suitable, for example, for single use.

The application surface 202 is heated by being brought, for example, into contact with or close to a hot surface, for example by introducing it into a case equipped with a heating means such as the case described previously with reference to FIGS. 8 and 9.

In the present text, the contents, unless specifically mentioned, are expressed on a weight basis relative to the total weight of the composition.

The invention is illustrated in greater detail in the examples described below, which are given as non-limiting illustrations. The percentages are weight percentages. In the examples that follow, the weight percentages are indicated relative to the total weight of the composition.

EXAMPLES Example 1 Lipstick Composition

A lipstick according to the invention was prepared, having the following composition:

Composition Phase Ingredients Function 1 (weight %) A OCTYLDODECANOL FATTY 5 SUBSTANCE DIISOSTEARYL MALATE FATTY 10 SUBSTANCE B POLYBUTENE (Indopol POLYMER 10 H 100 from INEOS) POLYESTER: Pentaeryth- POLYMER 20 ritol 20/benzoic acid 4/isostearic acid 56/ isophthalic acid 20 (as prepared in Example 2 of EP-A-1 870 082) C BIS-BEHENYL/ISO- FATTY 10 STEARYL/PHYTO- SUBSTANCE STERYL DIMER DI- LINOLEYL DIMER DILINOLEATE (Plandool G from Nippon Fine Chemical) BIS-DIGLYCERYL FATTY 14.72 POLYACYLADIPATE-2 SUBSTANCE (Softisan 649 from Sasol) POLYESTER of C36 FATTY 10 ACID DIMER and of SUBSTANCE HYDROGENATED CASTOR OIL (Risocast from Kokyu Alcohol Kogyo) D POLYETHYLENE FATTY 10 (Performalene 400 from SUBSTANCE New Phase Technologies) E BLUE 1 LAKE DYE 1.2 TITANIUM OXIDE DYE 2.63 RED 28 LAKE DYE 1.65 IRON OXIDE DYE 4.8 Total 100

Protocol:

In a first stage, the pigments of phase E are dispersed in part of phase A.

The rest of the liposoluble ingredients of phase B and C and the waxes of phase D are mixed together at a temperature of 100° C., followed by addition thereto of the ground material and the rest of phase A. The whole is mixed at a temperature of 100° C. until a thoroughly uniform mixture is obtained.

Finally, the composition is poured in a mould to give it the shape of a stick 11.06 mm in diameter. The mould is then placed in a freezer at −18° C.

The hardness of the stick at 20° C. is 124 Nm⁻¹.

Evaluation:

At room temperature (20° C.), the composition thus obtained, when it is applied to the lips, transfers very little and is very tacky (slides poorly on the lips and disintegrates with difficulty).

On the other hand, after heating the end of the stick (generally of bevelled shape), at 60° C. for 10 seconds, it is possible to apply the stick easily (with good glidance and easy disintegration) to the lips and to obtain a thick makeup deposit.

Furthermore, the makeup deposited on the lips with the preheated composition 1 shows improved remanence of the colour and also improved gloss when compared with the makeup deposit obtained with the same composition 1 that has not been heated, applied at room temperature (20° C.)

Example 2 Lipstick Composition

A lipstick according to the invention was prepared, having the following composition:

Composition 2 according to the invention Phase Ingredients Function (weight %) A OCTYLDODECYL PPG-3 FATTY 2.28 MYRISTYL ETHER DIMER SUBSTANCE DILINOLEATE (Liquiwax polyEFA OR from Arch Personal Care) TRIDECYL FATTY 2.28 TRIMELLITATE SUBSTANCE B Trimethyl 1,1,3,5,5- SILICONE 50.36  pentaphenyl trisilox- ane (PH-1555 HRI from Dow Corning) C POLYESTER: Pentaeryth- POLYMER 20   ritol 20/benzoic acid 4/isostearic acid 56/ isophthalic acid 20 (as prepared in Example 2 of EP-A-1 870 082) D HYDROGENATED COCO- FATTY 2   GLYCERIDES (Softisan SUBSTANCE 100 from SASOL) VINYL ACETATE/ALLYL POLYMER 3.95 STEARATE COPOLYMER (65/35) (Mexomer PQ from Chimex) POLYVINYL LAURATE POLYMER 5.92 (Mexomer PP from Chimex) POLYSTEARYL ACRYLATE POLYMER 2.96 (Intelimer IPA 13-1 from Air Products & Chemicals) E HYDROGENATED JOJOBA FATTY 2   OIL (Jojoba Wax Flakes SUBSTANCE from Desert Whale) MICROCRYSTALLINE WAX FATTY 3   (Base Wax 30540 from SUBSTANCE Paramelt) C30-50 ALCOHOLS SURFACTANT 1   (Performacol 550-L Alcohol from New Phase Technologies) F TITANIUM OXIDE DYE 1.37 YELLOW 6 LAKE DYE 1.29 RED 7 DYE 0.3  BLUE 1 LAKE DYE 0.08 BLACK IRON OXIDE DYE 0.16 G MICA-TITANIUM NACRE 1   DIOXIDE-BROWN IRON OXIDE FRAGRANCE FRAGRANCE 0.05 Total 100%  

Protocol:

In a first stage, the pigments of phase F are dispersed in part of phase A and part of phase B.

The rest of the liposoluble ingredients of phase C and D and the waxes of phase E are mixed together at a temperature of 100° C., followed by addition thereto of the ground material and the rest of phase B. The whole is mixed at a temperature of 100° C. until a thoroughly uniform mixture is obtained.

Finally, the composition is poured in a mould to give it the shape of a stick 11.06 mm in diameter. The mould is then placed in a freezer at −18° C.

The hardness of the stick at 20° C. is 117 Nm⁻¹.

Evaluation:

At room temperature (20° C.), the composition thus obtained, when it is applied to the lips, transfers very little and is very tacky (slides poorly on the lips and disintegrates with difficulty).

On the other hand, after heating the end of the stick (generally of bevelled shape), at 60° C. for 10 seconds, it is possible to apply the stick easily (with good glidance and easy disintegration) to the lips and to obtain a thick makeup deposit.

Furthermore, the makeup deposited on the lips with the preheated composition 2 shows improved remanence of the colour and also improved gloss when compared with the makeup deposit obtained with the same composition 2 that has not been heated, applied at room temperature (20° C.)

It is also observed that the makeup deposit produced with the preheated composition 2 shows, compared with that produced with the preheated composition 1, improved remanence of the colour, and also improved gloss immediately after application.

The above written description of the invention provides a manner and process of making and using it such that any person skilled in this art is enabled to make and use the same, this enablement being provided in particular for the subject matter of the appended claims, which make up a part of the original description.

As used herein, the words “a” and “an” and the like carry the meaning of “one or more.” The phrases “selected from the group consisting of,” “chosen from,” and the like include mixtures of the specified materials. Terms such as “contain(s)” and the like are open terms meaning ‘including at least’ unless otherwise specifically noted.

All references, patents, applications, tests, standards, documents, publications, brochures, texts, articles, etc. mentioned herein are incorporated herein by reference. Where a numerical limit or range is stated, the endpoints are included. Also, all values and subranges within a numerical limit or range are specifically included as if explicitly written out. 

1. A process for making up and/or caring for a non-fibrous human keratin material, comprising: bringing an outer surface of a piece of a solid cosmetic composition into contact with or close to a heating device so as to heat the piece locally in order to soften essentially only the outer surface of the solid cosmetic composition and to lower the solid cosmetic composition's coefficient of dynamic friction, and applying the thus heated outer surface of the composition to the non-fibrous human keratin material, wherein the solid cosmetic composition comprises, in a physiologically acceptable medium: (i) at least one polyester obtained by reacting: a tetraol containing from 4 to 10 carbon atoms; a linear or branched saturated monocarboxylic acid containing from 9 to 23 carbon atoms; a cyclic dicarboxylic acid containing from 6 to 12 carbon atoms; and an aromatic monocarboxylic acid containing from 7 to 11 carbon atoms, and (ii) at least one solid fatty substance chosen from waxes and pasty fatty substances.
 2. The process according to claim 1, in which the polyester(s) is obtained by reacting: from 10% to 30% by weight of a tetraol containing from 4 to 10 carbon atoms; from 40% to 80% by weight of a linear or branched saturated monocarboxylic acid containing from 9 to 23 carbon atoms; from 5% to 30% by weight of a cyclic dicarboxylic acid containing from 6 to 12 carbon atoms; from 0.1% to 10% by weight of an aromatic monocarboxylic acid containing from 7 to 11 carbon atoms, and the contents being expressed as weight percentages relative to the total weight of the polyester.
 3. The process according to claim 1, in which the polyester(s) are chosen from benzoic acid/isophthalic acid/isostearic acid/pentaerythritol polyesters, benzoic acid/isophthalic acid/stearic acid/pentaerythritol polyesters, and mixtures thereof.
 4. The process according to claim 1, in which the composition comprises at least two polyesters that are different from each other.
 5. The process according to claim 1, in which the composition comprises from 1% to 60% by weight of polyester relative to the total weight of the composition.
 6. The process according to claim 1, in which the composition further comprises at least one non-volatile oil.
 7. The process according to claim 1, in which the composition further comprises at least one oil with a molecular weight of greater than 500 g/mol.
 8. The process according to claim 1, in which the composition further comprises a phenyl silicone oil.
 9. The process according to claim 6, in which the oil is present in a content of 1% to 90% by weight relative to the total weight of the composition.
 10. The process according to claim 1, in which the solid cosmetic composition has a temperature-sensitive coefficient of dynamic friction greater than or equal to 0.5 at 25° C.
 11. The process according to claim 1, in which the solid cosmetic composition has a hardness of greater than or equal to 80 Nm⁻¹ at 20° C.
 12. The process according to claim 1, in which the locally heated surface of the composition is heated to a temperature where the coefficient of dynamic friction of the locally heated surface of the composition is less than or equal to 0.45.
 13. The process according to claim 1, in which the composition is in the form of a wand.
 14. The process according to claim 1, in which the keratin material is the lips and the composition is a lipstick.
 15. A kit comprising: a solid cosmetic composition comprising, in a physiologically acceptable medium: (i) at least one polyester obtained by reacting: a tetraol containing from 4 to 10 carbon atoms; a linear or branched saturated monocarboxylic acid containing from 9 to 23 carbon atoms; a cyclic dicarboxylic acid containing from 6 to 12 carbon atoms; and an aromatic monocarboxylic acid containing from 7 to 11 carbon atoms, and (ii) at least one solid fatty substance chosen from waxes and pasty fatty substances, and a heating device for locally heating a surface of a piece of the composition. 